SOLVENT-FREE SYNTHESIS OF BISFERROCENYLIMINES AND THEIR COORDINATION TO RHODIUM(I)

PHUMELELE ELDRIDGE KLEYI

Submitted in partial fulfilment of the requirements for the degree of MAGISTER SCIENTIAE in the Faculty of Science at the Nelson Mandela Metropolitan University

Supervisor: Co-Supervisors:

Prof. Christopher Imrie Prof. T. I. A. Gerber Prof. C. W. McCleland

January 2009

ACKNOWLEDGEMENTS
The author would like to express his gratitude to the following, for the contributions made in the thesis: 1. Dr. Christopher Imrie for guidance, support and encouragement throughout the project. 2. Prof. C. W. McCleland for help with NMR problems. 3. Prof. T. I. A. Gerber assistance with the project and thesis. 4. Dr. P. Mallon from the University of Stellenbosch for the help with Gel Permeation Chromatography. 5. Mr. Harold Marchand, Mr H. Schalekamp and Mr. J. Booi for technical assistance. 6. Mr. Irvin Booysen for assistance with UV-vis, CV and conductometry. 7. Mr. M. Mtyopo and Mr. B. Mpuhlu for assistance with GC. 8. Dr. E. R. T. Elago, Dr. V. O. Nyamori, Dr. Z. Tshentu and Mr. P. Hlangothi for friendly advice. 9. My colleagues, Mr. D. Onyancha and Mrs. N. Adams for friendship and support. My brother, Ayanda, for being there when I needed him most. 10. NRF and NMMU for financial support towards my studies. 11. Last but not least, The Almighty God for making my dreams come true.

ABSTRACT
Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene. Keywords: bisferrocenylimines, coordination chemistry, rhodium(I).

ii

PRESENTATIONS AND PUBLICATIONS

Publications Further solvent-free reactions of ferrocenylaldehydes: Synthesis of 1,1ferrocenyldiimines and ferrocenylacrylonitrile, C. Imrie, P. Kleyi, V. O. Nyamori, T. I. A. Gerber, D. C. Levendis and J. Look, J. Organomet. Chem., 692 (2007) 3443-3454. Conference proceedings Solvent-free synthesis and coordination chemistry of

diferrocenyldiazaalkanes, P. Kleyi, C. Imrie and C. W. McCleland, 37th International Conference on Coordination Chemistry (ICCC37), Cape Town, South Africa, August 2006. Ferrocenylnitrogen-donor ligands for homogeneous catalysis, P. Kleyi, D. Saku, C. Imrie and C. W. McCleland, 15th International Symposium on Homogeneous Catalysis (ISHCXV), Sun City, South Africa, August 2006. Synthesis and use of bisferrocenylimines as new catalysts for olefin polymerization, P. Kleyi, C. Imrie and C. W. McCleland, Inorganic Chemistry Conference (INORG007), Club Mykonos, Western Cape, South Africa, July 2007.

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CONTENTS
Page ACKNOWLEDGEMENTS ........................................................................................... i ABSTRACT ................................................................................................................ii PRESENTATIONS AND PUBLICATIONS ................................................................ iii LIST OF FIGURES................................................................................................... viii LIST OF SCHEMES ................................................................................................... x LIST OF TABLES ..................................................................................................... xii ABBREVIATIONS.................................................................................................... xiii

CHAPTER 1 ........................................................................................................... 1
INTRODUCTION ........................................................................................................ 1 1.1 Solvent-free synthesis ...................................................................................... 1 1.1.1 Background................................................................................................... 1 1.2 FERROCENES ................................................................................................... 5 1.2.1 Solvent-free synthesis of ferrocenes............................................................. 5 1.2.1.1 Synthesis of ferrocenylenones ............................................................... 6 1.2.1.2 Reaction of ferrocenecarboxaldehyde with methylene active compounds ............................................................................................................................ 7 1.2.1.3 Reaction of ferrocenecarboxaldehyde with an ylid ................................. 9 1.2.1.4 Synthesis of ferrocenyl-1,5-diketone derivatives .................................. 10 1.2.1.5 Synthesis of ferrocenoate esters .......................................................... 10 1.2.1.6 Synthesis of ferrocenylimines ............................................................... 11 1.3 SOLVENT-FREE SYNTHESIS OF LIGAND SYSTEMS................................... 12 1.4 NITROGEN-DONOR LIGAND CHEMISTRY .................................................... 17 1.4.1 Polymerization reactions ............................................................................. 19 1.4.2 Cross-coupling reactions ............................................................................ 22 1.4.2.1 Heck reactions ..................................................................................... 22 1.4.2.2 Suzuki cross-coupling reactions ........................................................... 24 iv

1.4.3 Epoxidation reactions ................................................................................. 26 1.4.4 Asymmetric allylic substitution reactions ..................................................... 29 1.4.5 Ring-opening metathesis polymerization (ROMP) ...................................... 30 1.5 FERROCENYL-NITROGEN DONOR LIGAND CHEMISTRY........................... 32 1.5.1 Ferrocenyl-pyridine ligands ......................................................................... 32 1.5.2 Ferrocenyl-Schiff base ligands.................................................................... 36 1.6 OBJECTIVES OF THE PROJECT.................................................................... 40 1.7 REFERENCES .................................................................................................. 41

CHAPTER 2 ......................................................................................................... 50
RESULTS AND DISCUSSION ................................................................................ 50 2.1 SOLVENT-FREE SYNTHESIS OF BISFERROCENYLIMINES........................ 50 2.1.1 Introduction ................................................................................................. 50 2.1.2 Synthesis and characterization of bisferrocenyimines ................................ 51 2.1.3 Solvent-free synthesis of arylbisimines ....................................................... 57 2.2 REDUCTION REACTION OF BISFERROCENYLIMINES .............................. 60 2.2.1 Reduction of bisferrocenylimines ................................................................ 60 2.2.2 Reduction of arylbisimines .......................................................................... 63 2.3 ELECTRONIC SPECTROSCOPY .................................................................... 63 2.4 CYCLIC VOLTAMMETRY ................................................................................ 66 2.5 EXPERIMENTAL .............................................................................................. 68 2.5.1 Purification procedures ............................................................................... 68 2.5.2 Instrumentation ........................................................................................... 69 2.6 SYNTHESIS OF BISFERROCENYLIMINES AND ARYLBISIMINES .............. 70 2.6.1 General procedure for the synthesis of bisferrocenylimines ....................... 70 2.6.2 Reduction of bisferrocenylimines and arylbisimines ................................... 75 2.7 REFERENCES .................................................................................................. 79 v

CHAPTER 3 ......................................................................................................... 80
RESULTS AND DISCUSSION ................................................................................ 80 3.1 SYNTHESIS OF CATIONIC RHODIUM(I) COMPLEXES ................................. 80 3.1.1 Rhodium(I) complexes containing bisferrocenylimines ............................... 80 3.1.2 X-ray Crystallography ................................................................................. 84 3.1.3 Rhodium(I) complexes containing bisferrocenylamines .............................. 89 3.2 ELECTRONIC SPECTROSCOPY .................................................................... 93 3.3 CYCLIC VOLTAMMETRY ................................................................................ 95 3.4 EXPERIMENTAL .............................................................................................. 97 3.4.1 Purification procedures ............................................................................... 97 3.4.2 Instrumentation ........................................................................................... 97 3.5 SYNTHESIS OF RHODIUM(I) COMPLEXES ................................................... 98 3.5.1 Rhodium(I) complexes containing bisferrocenylimines ............................... 98 3.5.1.1 General procedure3 .............................................................................. 98 3.5.2 Rhodium(I) complexes containing bisferrocenylamines ............................ 100 3.6 REFERENCES ................................................................................................ 102

CHAPTER 4 ....................................................................................................... 103

RESULTS AND DISCUSSION .............................................................................. 103 4.1 POLYMERIZATION OF PHENYLACETYLENE ............................................. 103 4.1.1 Introduction ............................................................................................... 103 4.1.2 Polymer characterization .......................................................................... 104 4.2 CATALYTIC POLYMERIZATION STUDIES .................................................. 105 4.2.1 Spectroscopic properties of polymers ....................................................... 106 4.2.2 Thermal analysis....................................................................................... 108 4.2.3 Mechanistic pathways for polymerization of phenylacetylene ................... 109

vi

4.3 HYDROFORMYLATION OF STYRENE ......................................................... 111 4.3.1 Introduction ............................................................................................... 111 4.3.2 Catalytic hydroformylation studies ............................................................ 113 4.3.3 Mechanism for hydroformylation of styrene .............................................. 115 4.4 EXPERIMENTAL ............................................................................................ 117 4.4.1 Purification procedures ............................................................................. 117 4.4.2 Instumentation .......................................................................................... 117 4.4.3 Polymerization of phenylacetylene ........................................................... 117 4.4.4 Hydroformylation of styrene ...................................................................... 118 4.5 REFERENCES ................................................................................................ 118

CHAPTER 5 ....................................................................................................... 121

CONCLUSION ....................................................................................................... 121 5.1 Conclusion ...................................................................................................... 121

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LIST OF FIGURES
Page Figure 1.1: DSC analysis of ferrocenecarboxaldehyde ............................................ 6 Figure 1.2: Some N-donor ligands with sp2-hybridised nitrogen atoms .................. 18 Figure 1.3: Bis(alkylphenylaminopyridinato) titanium complexes ........................... 20 Figure 1.4: Pyridyl-imine complexes of iron (Fe) and palladium (Pd) ..................... 21 Figure 1.5: Examples of Pd-pyridyl complexes used for the Heck reactions .......... 23 Figure 1.6: Examples of Ni(0) complexes used for cross-coupling of arylchlorides. ................................................................................................................................. 24 Figure 1.7: Palladium imine and amine complexes for coupling of aryl bromides .. 26 Figure 1.8: Three isomers of Ru(pap)2Cl2 .............................................................. 27 Figure 1.9: Mn(III) Schiff-base complexes for electrocatalytic epoxidation of olefins ................................................................................................................................. 28 Figure 1.10: Figure 1.11: Figure 1.12: Figure 1.13: Figure 1.14: Figure 1.15: Figure 1.16: Figure 1.17: Figure 1.18: Figure 1.19: Figure 1.20: Figure 1.21: Figure 1.22: Figure 1.23: Figure 1.24: The cis- isomer of the binaphthyl-bridged Schiff base titanium complex .......................................................................................... 28 Example of chiral bidentate thiazolyl-pyridine ligands30 Chiral diimine palladium(II) catalyst for asymmetric alkylation ........ 30 The reaction pathway of ROMP ...................................................... 31 Re and Pt complexes with ferrocenylpyridine ligands ..................... 33 Tungsten complexes with ferrocenylpyridine ligands ...................... 33 Examples of ferrocenylpyridyl and pyrimidyl complexes ................. 34 Pd and Pt complexes of 1,1-bis(2-pyridyl)ferrocene ....................... 34 Palladium and nickel complexes ..................................................... 35 Dimeric cyclopalladated ferrocenylimine complex for catalytic Heck reaction ........................................................................................... 36 Cyclopalladated ferrocenylimine for Mirozoki-Heck reaction ........... 37 1,1-N-substituted ferrocenediyl Pd(II) complex for Suzuki crosscoupling reaction ............................................................................. 37 Dimeric cyclopalladated ferrocenylketimine complexes for Suzuki reaction ........................................................................................... 38 Chiral ferrocenylphosphine-imine ligand ......................................... 38 Cationic Rh(I) and Ir(I) complex for olefin polymerization ................ 39

viii

Figure 1.25: Figure 2.1:

Cationic Rh(I) complexes for hydroformylation reactions. ................ 40 General structure of bisferrocenylimines to be synthesized ............. 51 of the solvent-free synthesis of N,Noctylenebis(ferrocenylmethylidine)amine ........................................ 52

Figure 2.2: The pictorial stages Figure 2.3: Figure 2.4: Figure 2.5: Figure 2.6: Figure 2.7: Figure 2.8: Figure 2.9: Figure 3.1: Figure 3.2: Figure 3.3: Figure 3.4: Figure 3.5: Figure 3.6: Figure 3.7: Figure 3.8: Figure 3.9:

IR spectrum of [2.5].......................................................................... 54
1

H NMR spectrum of [2.5] ................................................................. 55 C NMR spectrum of [2.8] ................................................................ 60

13

UV-vis spectrum of unsubstitued ferrocene in dichloromethane. ...... 64 UV-vis spectra of bisferrocenylimines in dichloromethane. ............... 65 UV-vis spectra of bisferrocenylamines in dichloromethane. .............. 65 Cyclic voltammogram of ferrocene in acetonitrile. ............................. 67
1

Figure 2.10: Cyclic voltammograms of [2.2], [2.5], [2.12] and [2.14]. ................... 67 H NMR spectra of [3.2] (top) and [3.3] (bottom) in CDCl3................ 83 ORTEP diagram of [3.2].................................................................... 85 Crystal packing of [3.2], projection viewed along [100] ..................... 87 ORTEP drawing of [3.3] .................................................................... 88 Crystal packing of [3.3], projection viewed along [100]. .................... 88 Cationic rhodium(I) diamine complexes with the [Rh(COD)Cl2]- anion. Cationic rhodium(I) complexes ........................................................... 90 IR spectrum of [3.5] ........................................................................... 91 IR spectrum of [3.8] ........................................................................... 93

................................................................................................................................. 89

Figure 3.10: UV-vis spectra of [3.1], [3.2] and [3.3]. .............................................. 94 Figure 3.11: UV-Vis spectra of [3.4], [3.5] and [3.6] .............................................. 94 Figure 3.12: UV-vis spectra of [3.7] and [3.8]. ....................................................... 95 Figure 3.13: Cyclic voltammograms of [3.2], [3.4], [3.5] and [3.6] ......................... 96 Figure 4.1: Figure 4.2: Figure 4.3: Figure 4.5: Stereoisomers of polyphenylacetylene ............................................. 104
1

H NMR spectrum of PPA, catalyzed by [3.2]. ................................. 107

IR spectrum of PPA prepared using [3.2]......................................... 108

1

Figure 4.4: TGA and DSC curves of PPA obtained with [3.1]. ............................ 109 H NMR spectrum of the products of hydroformylation of styrene catalyzed by [3.6] .............................................................................. 114

ix

LIST OF SCHEMES
Page Scheme 1.1: Examples of solvent-free reactions .................................................... 3 Scheme 1.2: Solvent-free synthesis of 3-carboxycoumarins ................................... 3 Scheme 1.3: Photoirradited solvent-free dimerization of cholest-4-en-3-one .......... 4 Scheme 1.4: Solvent-free synthesis of ferrocenylenones ........................................ 7 Scheme 1.5: Solvent-free Knoevenagel condensation reaction .............................. 8 Scheme 1.6: Solvent-free Wittig reaction of ferrocenecarboxaldehyde ................... 9 Scheme 1.7: Solvent-free synthesis of ferrocenyl 1,5-diketone derivatives ........... 10 Scheme 1.8: Solvent-free synthesis of ferrocenoate esters .................................. 11 Scheme 1.9: Solvent-free reactions of ferrocenylaldehydes with aromatic amines 11 Scheme 1.10: Synthesis of binaphthol .................................................................... 12 Scheme 1.11: Solvent-free palladium-catalyzed phosphination reaction................. 13 Scheme 1.12: Solvent-free oxidation of thiols to disulfides...................................... 13 Scheme 1.13: A mechanism for the synthesis of unsymmetrical sulfides from thiols and alkyl halides using hydrotalcite clays.......................................... 14 Scheme 1.14: Solvent-free metal mediated synthesis of homoallyl alcohols........... 14 Scheme 1.15: Microwave assisted solvent-free synthesis of -aminoalcohols........ 15 Scheme 1.16: Sc(OTf)3 catalyzed solvent-free synthesis of -aminoalcohols ......... 15 Scheme 1.17: Solvent-free synthesis of tetrasubstituted imidazoles on silica gel support ............................................................................................ 16 Scheme 1.18: Solvent-free synthesis of tetrasubstituted imidazoles on SiO2/NaHSO4 support .............................................................................................. 16 Scheme 1.19: Solvent-free synthesis of 2,4,6-triarylpyridines ................................. 17 Scheme 1.20: Solvent-free synthesis of Schiff bases .............................................. 17 Scheme 1.21: Synthesis of bis(phenoxyketimine) zirconium complexes ................. 20 Scheme 1.22: Synthesis of silica-supported imine palladacycles. ........................... 25 Scheme 1.23: Suzuki cross-coupling of aryl bromides with phenylboronic acid. ..... 26 Scheme 1.24: Allylic alkylation of 1,3-di[henyl-2-enyl acetate with dimethyl malonate ................................................................................................................................. 29 Scheme 1.25: Synthesis of Ru complexes derived from 1st generation Grubbs catalyst. ........................................................................................... 32 x

Scheme 1.26: Synthesis of N-ferrocene salicylaldimine ligand ............................... 39 Scheme 2.1: Solvent-free synthesis of ferrocenylimines ......................................... 50 Scheme 2.2: Solvent-free synthesis of bisferrocenylimines ..................................... 51 Scheme 2.3: Solvent-free synthesis of arylbisimines in the presence of a catalyst. 57 Scheme 2.4: Solvent-free synthesis of arylbisimines............................................... 58 Scheme 2.5: Hydrogenation of ferrocenylbisimines. ............................................... 61 Scheme 3.1: Procedure for the synthesis of cationic rhodium(I) complexes. .......... 81 Scheme 4.1: Polymerization of phenylacetylene with Rh(I) catalysts. ................... 105 Scheme 4.2: Insertion mechanism for polymerization of phenylacetylene ............ 110 Scheme 4.3: Metallacyclic mechanism for the polymerization of phenylacetylene 110 Scheme 4.4: Hydroformylation of olefins. .............................................................. 111 Scheme 4.5: Synthesis of precursor to the indolizidine alkaloid ............................ 113 Scheme 4.6: Hydroformylation of styrene catalyzed by [3.4]-[3.8] ........................ 113 Scheme 4.7: Possible mechanism for hydroformylation of styrene catalyzed by [3.4][3.8] ................................................................................................... 116

xi

LIST OF TABLES
Page Table 2.1: Yields of bisferrocenylimines from the solvent-free reaction of diamines and ferrocenecarboxaldehyde ............................................................... 53 Table 2.2: Chemical shifts for protons on the carbon directly bonded to nitrogen group. .................................................................................................... 56 Table 2.3: Yields of arylbisimines from a reaction of substituted benzaldehyde and ethylenediamine .................................................................................... 59 Table 2.4: Yields of bisferrocenylimines .................................................................. 62 Table 2.5: UV-vis data for ferrocene, [2.1]-[2.5] and [2.10]-[2.14]. ......................... 66 Table 2.6: Half-wave potentials of [2.1]-[2.5] and [2.12]-[2.14]. .............................. 68 Table 3.1: The summarized NMR data for [3.1]-[3.3]. ............................................. 82 Table 3.2: Crystal data and structure refinement of [3.2] and [3.3]. ....................... 84 Table 3.3: Selected bond distances, bond angles and torsion angles of [3.2] ......... 86 Table 3.4: Selected bond distances, bond angles and torsion angles of [3.3] ......... 89 Table 3.5: Table of yields and conductivity measurements...................................... 92 Table 3.6: UV-vis data for complexes [3.1]-[3.8]. .................................................... 95 Table 3.7: Half-wave potentials of [3.1]-[3.6]........................................................... 96 Table 4.1: Polymerization of phenylacetylene with Rh(I) complexes. .................... 106 Table 4.2: Determination of cis-content of polymers .............................................. 108 Table 4.3: Hydroformylation of styrene catalyzed by rhodium(I) complexes .......... 115

xii

ABBREVIATIONS
ca. cat COD Cp CDCl3 DSC EI FAB J Lit. M+ MeOH M.p. NMR Ph PP PPA ppm RT Angstrom approximately catalyst 1,5-cyclooctadiene cyclopentadienyl, C5H5 deuterated chloroform degree differential scanning calorimetry extinction coefficient electron impact fast atom bombardment coupling constant literature parent molecular ion methanol melting point nuclear magnetic resonance phenyl phenylpropanal poly(phenylacetylene) parts per million room temperature

xiii

CHAPTER 1 INTRODUCTION

1.1 Solvent-free synthesis

1.1.1 Background Chemistry has played a leading role in changing peoples lives, due to its impact in areas such as agrochemicals, the clothing industry, food technology, energy and transport, the pharmaceutical industry and most recently in the manufacture of electronic devices. However, discoveries about ecotoxic effects such as endocrine disruption1 indicated that synthetic chemicals released into the environment have a negative impact on the world ecosystem. Industrial incidents involving explosions at a major South African petrochemical company,2,3 the discovery of persistent organic pollutants and the global warming are examples of chemical disasters. It is because of this reason that chemists are compelled to shoulder the responsibility for the consequences and thus develop new synthetic protocols that are environmentally benign. These new synthetic protocols should comply with green chemistry principles.4 As an alternative to organic solvents, chemists should employ other strategies to perform chemical reactions, namely ionic liquids, supercritical fluids, water as a solvent and solvent-free conditions. Conventionally, chemical transformations have been carried out in the presence of a solvent to provide a homogeneous medium for the reagents to interact effectively as well as for the isolation and purification of the desired product.5,6 It was believed that in solution the reagents have higher mobility, hence increased molecular collisions leading to faster chemical reactions. Unfortunately, organic solvents are high on the list of toxic or hazardous compounds because of large volumes used in industry, and difficulties in containing volatile organic compounds (VOCs).7

The development of solvent-free organic synthetic procedures has become an important and popular research area.8 Chemical reactions under solvent-free conditions have been practised for many years. It has been reported that the first written document on a solvent-free reaction came from a book De Lapidibus by Theophrastus (371-286 B.C).9 He reported that when cinnabar (HgS) was ground in a brass motor with a brass pestle in the presence of vinegar, metallic mercury was obtained. Afterwards, reports on chemical transformations under solvent-free medium were rare, until the work of Carey Lea10,11 as well as Ling and Baker at the end of the 19th century.12 Ling and Baker were successful in preparing quinhydrone by grinding together two solids. It was again only more than half a century later that researchers became interested in chemical transformations in the absence of a solvent medium. In the 1960s, Rastogi et al.13-15 carried out detailed investigations about factors governing the reaction between two solids, such as mobility on the interface, kinetics and mechanism. In 1984, Patil et al.16 reported on the successful solvent-free synthesis of unsymmetrically substituted quinhydrones, which was an alternative to the problematic solution procedure due to self-oxidation reactions. In 1987, Toda et al.17 introduced the concept of host-guest complex formation in the solid state. It was proposed that the quinine sublimes and its vapour attacks certain hydroquinone sites. Toda et al.18,19 went on to report on their successful Grignard reaction and aldol condensation under solvent-free conditions. Owing to these successes, many researchers began to recognise the advantages of carrying out chemical reactions in the absence of solvents. In the 1990s, researchers became strongly involved in carrying out studies on different types of reactions without the use of classical solvents. Examples were the work of Kaupp et al. (1993)20 (Scheme 1.1a), Villemin et al. (1995)21 (Scheme 1.1b) and Ranu et al. (1997)22 (Scheme 1.1c) as well as other researchers.23-25 Ranu and coworkers were successful in synthesizing a Michael addition type product under microwave-assisted solvent-free conditions.

a) O

R' N S R N H R'' S N O H
100%

+
R''

solvent-free

N H

R'

(i) R = R' = R'' = H (ii) R = R' = H, R" = CH3 (iii) R = R'' = H, R' = Ph b) CH3 N R CHO + O O O N H Cl NH Solvent-free MW O H R

CH3 N NH N H
84-91%

R=

c) O R O + R'

O Al2O3

O n

MW

O R O R'
78-90%

(i): R =CH3; R' = OEt; n = 1, 2 (ii): R, R' = CH3; n = 1,2

Scheme 1.1: Examples of solvent-free reactions

20-22

In 2000, Scott and Raston26 reported on the synthesis of 3-carboxycoumarins, via the Knoevenagel condensation reaction, by gently grinding the starting materials in a mortar with a pestle (Scheme 1.2).
R OH + CHO O O R OH O O

O O NH 4 + MeCO 2 O O

O OH

R OH O

Scheme 1.2: Solvent-free synthesis of 3-carboxycoumarins26

DellaGreca et al27 reported, a year later, that it is possible to dimerize cholest-4-en3one under photoirradiation. Powdered cholest-4-en-3-one was simply irradiated with a UV lamp to yield the desired product (Scheme 1.3).

OH hv O

OH

Scheme 1.1: Photoirradited solvent-free dimerization of cholest-4-en-3-one27 Solvent-free reactions are of utmost interest from the ecological point of view, and they offer advantages, such as reduced reaction times, increased product yields, reduced environmental pollution, simple equipment (lab scale), increased selectivity, and low cost compared with reactions carried out in solvents.4 The formation of hot spots (solvents can act as heat sinks) and the prospects of runaway reactions is one of the few disadvantages of the solvent-free reactions. Another disadvantage is the difficulty in designing suitable reactors for these reactions to be applied in the industrial scale.4 However, these problems can be solved by using engineering reactor technology.7

1.2 Ferrocenes
1.2.1 Solvent-free synthesis of ferrocenes The discovery and characterization of the structure of ferrocene or cyclopentadienyl iron, Fe(C5H5)2 in the early 1950s,28 led to an explosion of interest in d-block metalcarbon bonds and stimulated the development of organometallic chemistry.29-33 Ferrocene derivatives are extremely important since they can be used in a variety of functions, such as the synthesis of non-linear optical materials, organometallic complexes, and in catalysis.34-37 However, the preparation of ferrocene derivatives has usually been performed under homogeneous conditions in the presence of classical solvents. With the current upsurge of interest in performing chemical transformations under solvent-free reactions, researchers have successfully prepared ferrocene derivatives under solvent-free conditions. In general, the reaction is induced by a method of mechanochemical activation.38-40 This merely means mechanical mixing (grinding or stirring) of the chemical reagents to bring about the reaction at room temperature. In some cases, this is coupled with microwave irradiation,41 especially to accelerate reactions that are very slow at room temperature. A mortar and pestle set is used for simple mechanical mixing and a commercial microwave oven for irradiation. It is worth noting that after reviewing the literature, it is apparent that most of the solvent-free reactions of ferrocenes reported are carbonyl condensation reactions, particularly the two compounds, ferrocenecarboxaldehyde35-37,41-44 and acetylferrocene.41,43 These two compounds are important precursors for numerous ferrocene derivatives, and have been shown to be particularly amenable to reactions under solvent-free conditions.41-44,47 Differential scanning calorimetry (DSC) analysis (Figure 1.1)42 indicates that ferrocenecarboxaldehyde exhibits a phase transition, called a plastic crystal phase, at 45 and runs to its melting point at 120 This C C. phase transition is considered to a point where a reaction takes place. Acetylferrocene is expected to be less reactive due to the lack of this phase transition and also due to steric hindrance by the methyl group.

Figure 1.1: DSC analysis of ferrocenecarboxaldehyde We shall now consider the solvent-free reactions of ferrocenes and comparisons with other synthetic methods will be provided where possible.

1.2.1.1 Synthesis of ferrocenylenones The synthesis of ferrocenylenones can be performed by a variety of methods, such as Claisen-Schmidt41 and aldol reactions43,44 under homogeneous conditions in ethanol. Other methods that have been reported include the use 18-crown ether as a phase-transfer catalyst (PTC) and solvent-free aldol reactions using pulverized potassium hydroxide.41,43 In 1994, Villemin and co-workers41 described the solventfree synthesis of ferrocenylenones under microwave irradiation conditions. Acetylferrocene was stirred with an aromatic aldehyde and ferrocenecarboxaldehyde was stirred with a ketone, in the presence of a base or a phase-transfer catalyst (Aliquat 336), or both, under microwave irradiation, to achieve the corresponding ferrocenylenone (Scheme 1.4).

O C Fe R Ar

O KOH, A336 H RT or MW Fe C C H H C Ar

R = H, CH3

Scheme 1.4: Solvent-free synthesis of ferrocenylenones41 However, this method suffers from a serious disadvantage,41,43 since it was found that the ferrocene derivatives combust easily in the microwave oven. Consequently, Liu et al.43 and Mndez et al.44 described an improved method for the preparation of ferrocenylenones via aldol condensation under solvent-free conditions. Mndez and co-workers performed the aldol reaction by adding powdered base to a stirred mixture of the reagents mixture in the presence of a PTC (Aliquat 336) while Liu et al. managed to achieve excellent yields of the products, in the absence of the PTC, by grinding a ketone and base using a mortar and pestle. Thereafter, the appropriate aldehyde was introduced with further grinding for a few minutes. Interestingly, all products formed for the different methods have an E-configuration as a major product.41-44

1.2.1.2

Reaction of compounds

ferrocenecarboxaldehyde

with

methylene

active

Knoevenagel condensation of ferrocenecarboxaldehyde with methylene active compounds is usually performed under classical homogeneous conditions in ethanol.36,37 Of the two isomers obtained, the E-isomer was found to possess more enhanced non-linear optical (NLO) properties than the Z-isomer.35 Incidentally, a whole range of these kinds of ferrocene derivatives have been studied for their NLO properties.35,36 They have also been used as catalysts for the combustion of composite explosives.37 The classical homogeneous methods frequently result in low yields and some reactions require the use of Schlenk techniques.36

O C Fe H X-CH2-Y, Al2O3 solvent-free Fe

H C

C
X
58-100%

X, Y = electron withdrawing group

Scheme 1.5: Solvent-free Knoevenagel condensation reaction36

Cooke and co-workers36 have reported on the solvent-free synthesis of novel ferrocene derivatives from the Knoevenagel condensation reaction of ferrocenecarboxaldehyde with methylene active compounds, in the presence of an inorganic support (Scheme 1.5). The role of the inorganic support, basic alumina in this case, was to increase the surface area and thus improve the conversion of reagents into the desired products. The reaction was carried out simply by grinding or stirring (depending on the nature of the methylene active compound) of the reaction mixture (at room temperature or heated up to 65C) and the consequent addition of a carefully calculated amount of basic alumina. This was accompanied by an immediate colour change to purple, indicating formation of the product. Isolation of the product was achieved simply by extraction with dichloromethane and in some cases further purification by column chromatography was necessary. Stankovic and co-workers35 obtained better yields, in some cases, when silica was used as an inorganic support and they postulated that due to the inherent acidity of the silica, it acted as a catalyst. It is worth mentioning that the method used by Stankovic and coworker differs to the one used by Cooke and coworkers. in that they do not grind the starting reagents. Instead, a solution of ferrocenecarboxaldehyde in dichloromethane is added to the inorganic support, followed by evaporation of the solvent. A solution of methylene active compound in dichloromethane is then added and the solvent evaporated. At this stage the reaction is left to stand at room temperature. The method of Stankovic takes longer (1-48 h) than that of Cooke (1-5 h), and yet there is difference in the yields. Bai et al.37 have reported on three methods for the Knoevenagel condensation of ferrocenecarboxaldehyde and the methylene active compound, namely in water, grinding under solvent-free conditions and microwave induced solvent-free reactions. All the methods are performed in the presence of 8

potassium hydroxide. Most interestingly all the methods had shorter reaction times than the previous methods, with reaction times in water (45 min), grinding (12-30 min) and microwave irradiation (6-8 min). None of the three methods was superior in terms of the product yields, although microwave assisted reactions had shorter reaction times.

1.2.1.3 Reaction of ferrocenecarboxaldehyde with an ylid

O C Fe H RCH2P+Ph3XSolvent-free, NaOH R = Ar X = Cl, Br, I
71-95%

H C Fe

CHR

Scheme 1.6: Solvent-free Wittig reaction of ferrocenecarboxaldehyde47 The Wittig reaction is a very popular method for the regio- and stereo-selective formation of alkenes from carbonyl compounds.45,46 A resonance-stabilized phosphonium intermediate, called an ylid, is generated by abstraction of a proton from a phosphonium salt by a base. The reaction of the ylid with a carbonyl group results in the formation of an alkene and triphenylphosphine oxide as a by-product. The Wittig reaction and many other synthetic methods used for the synthesis of vinylferrocene derivatives, have usually been performed in classical homogeneous media. The first ever solvent-free Wittig reaction was reported in 2001, by Liu and co-workers.47 They were successful in preparation of vinylferrocene by grinding ferrocenecarboxaldehyde and triphenylphosphinylbenzylphosphonium chloride in the presence of a sodium hydroxide, using a mortar and pestle (Scheme 1.6). The reactions were performed at room temperature (5 min) and slow reactions were heated at 65 C (40-45 min). The conversions of starting reagent were moderate to excellent and the major products were E-alkenes.

1.2.1.4 Synthesis ferrocenyl-1,5-diketone derivatives 1,5-Diketones are very useful synthetic intermediates and are desirable starting materials for the preparation of heterocyclic and polyfunctional compounds.48-50 These compounds have potential applications in coordination chemistry, molecular sensing, catalytic reactions, the chemical modification of electrodes and redox active self-assembly devices. Various procedures have been reported for the synthesis of 1,5-diketones, but require the use of expensive reagents, are carried out under refluxing conditions, and have longer synthetic routes.
O PhCOMe, NaOH R Fe solvent-free Fe Ph O R O

R = Ar

68-92%

Scheme 1.7: Solvent-free synthesis of ferrocenyl 1,5-diketone derivatives51 Liu and co-workers51 have reported on the solvent-free synthesis of 1,5-diketone derivatives containing ferrocene via the Michael addition reaction (Scheme 1.7). The reaction was performed by grinding a mixture of an ,-unsaturated ferrocenyl ketone (or ferrocenylchalcone) and acetophenone with an agate mortar and pestle, and the reaction mixture heated at 45 C. The pure products were obtained after a short and simple work-up procedure.

1.2.1.5 Synthesis of ferrocenoate esters Elago et al.52 have recently reported on the synthesis of ferrocenoate esters, amides and other ferrocenoyl derivatives in ionic liquids and under solvent-free conditions (Scheme 1.8). Both methods yielded excellent yields irrespective of the nature of the substituent X. However, the ionic liquid required deaeration and three cycles of freeze-thaw degassing. Moreover, the reaction requires 16 hours of stirring. In the solvent-free method ferrocenoyl fluoride and the appropriate substituted phenol were thoroughly ground in a mortar, and the mixture subjected to microwave irradiation for 1 minute. 10

O C Fe F X

O DMAP, [bmim][BF4] RT, 16 h or solvent-free, MW

X = 4-OCH3 = 4-CH3 = 4-H = 4-Cl = 4-NO2 = 4-Br = 4-CHO 60-100%

C Fe

O X

HO

Scheme 1.8: Solvent-free synthesis of ferrocenoate esters52

1.2.1.6 Synthesis of ferrocenylimines Several research groups53-55 have prepared ferrocenylimines by heating a solution of ferrocencarboxaldehyde with aromatic amines under reflux in anhydrous methanol or ethanol. Ferrocenylimines have been used for metal coordination and have also been studied for non-linear optical properties.56 The major setback with the solvent procedure is the decomposition of the imines during the heating process, leading to moderate yields. In highlighting the solvent-free procedure, Nyamori et al.42 have successfully prepared ferrocenylimines under solvent-free conditions (Scheme 1.9). Grinding of a mixture of ferrocenecarboxaldehyde and the appropriate substituted aniline with a glass rod in a glass tube resulted in excellent yields of products. The products were purified by recrystallization from a minimal amount of cold anhydrous methanol. In cases where the aniline substituent was an electron-withdrawing group or where the ferrocenecarboxaldehyde was less reactive, gentle heating (50 C) was necessary to obtain good conversions.

O Y Fe C H

N H2 N X Grind Solvent-free Fe Y C X H

87-97%

Y = Ph, Ph-Ph, Ph-O-Ph

Scheme 1.9: Solvent-free reactions of ferrocenylaldehydes with aromatic amines42 11

1.3 Solvent-free synthesis of ligand systems

It is generally accepted that a metal complex is a chemical species which contains a metal atom or ion bonded to a greater number of ions or molecules than would be expected from simple valency considerations.57 The ions or molecules that are bonded or coordinated with the metal are termed ligands. A ligand is regarded as an ion or a molecule that has a pair of electrons that it can easily donate. The actual atom through which a ligand is bonded to a metal is called the ligand atom. Ligands have played an extremely important role in human lives due to their use in various types of functions, such as in the synthesis of biologically active organometallic compounds58-62 and in catalysis.63-65 However, the synthesis of the ligands has always been performed in the presence of a solvent medium. For example, binaphthols have been prepared from 2-naphthol in the presence of a catalyst, oxygen or air as an oxidant and chlorinated solvents (Scheme 1.10).66,67
R2 R2
CuCl(OH).TMEDA (1mol%)

R1 R1

OH OH

O 2, CH 2 Cl2

R1

OH

R2

Scheme 1.10: Synthesis of binaphthol

66

Many research groups68-71 have reported on the synthesis of several kinds of phosphorus ligands in solution. Some methods required the use of very toxic reagents, such as potassium cyanide,70 working at very low temperature71 and many reaction steps. Therefore, in order to maintain the concept of sustainable chemistry the design of new synthetic procedures that are benign to the environment became a necessity. In this case special attention is given to the solvent-free approach to the synthesis of ligands. A good example of the solvent-free approach is that described by Kwong et al.72 on the phosphination reactions (Scheme 1.11). In that work, arylbromides and triflates were converted into the corresponding arylphosphines by palladium catalyzed 12

phosphination with triphenylphosphine under solvent-free conditions. Altough the yields were an improvement on those reported previously,73 they were still modest.
2.3 eq. PPh 3 10 mol% Pd(OAc)2 solvent-free, 115C

Y X

Y PPh 2

X = Br, OTf Y = CN, OMe, CHO, COCH 3, CO 2Me

Scheme 1.11: Solvent-free palladium-catalyzed phosphination reaction72 Another interesting example from the green chemistry perspective is the oxidation of thiols to disulfides. Thiols and disulfides play an important role in biological processes.74 Lenardo et al.75 discovered a solid-supported catalyst (Al2O3/KF) for the solvent-free oxidation of thiols to disulfides (Scheme 1.12). The reactions were performed either at room temperature, by gently heating or by microwave irradiation. Without any exception, the microwave assisted reactions proceeded faster and with higher yields.
Al2O3/KF (40%) RT, or MW

R = Ar = n-C12H25 = HO(CH2)2

48-96%

Scheme 1.12: Solvent-free oxidation of thiols to disulfides75

Vijaikumar and Pitchumani76 have also demonstrated the benefits of the solvent-free approach in the synthesis of unsymmetrical sulfides from thiols and alkyl halides using hydrotalcite clays (HT). The proposed mechanism is shown in Scheme 1.13.

13

HX

HT + OH -

RSH

H 2O HT + X RS - HT +

RSR'

R'S

Scheme 1.13: A mechanism for the synthesis of unsymmetrical sulfides from thiols

and alkyl halides using hydrotalcite clays76 McCluskey77 developed a method for allylation of carbonyl compounds by tetraallylstannane in the presence of water as a solvent. This procedure successfully minimised the environmental impact of tetraallylstannane by allowing the isolation of inorganic stannane salts and recycling the organic solvents used to extract the homoallylic alcohol products. A more recent method for allylation of carbonyl compounds is that reported by Andrews et al.78 This involves the synthesis of homoallylic alcohols via a metal-mediated reaction of carbonyl compounds with allyl bromide under solvent-free conditions (Scheme 1.14). In some cases the reactions are heated or subjected to sonification, and also require quenching of the reaction with water.
O
Br

+
R R'

i) M ii) H2O

R R'

OH

M = In, Bi, Zn, Cu R, R' = H, Aryl, Alkyl

0-97%

Scheme 1.14: Solvent-free metal mediated synthesis of homoallyl alcohols78

Sabitha et al.79 have also shown that the aminolysis of epoxides with ammonium acetate can proceed efficiently and regioselectively under solvent-free conditions, especially when subjected to microwave irradiation (Scheme 1.15). This procedure is

14

faster and results in higher yields than the corresponding solvent-mediated methods. The regioselectivity stems from the preferential attack of the nucleophile on the less hindered carbon atom of the epoxide ring.
OH R major NH 2

O R

NH 4 OAc, MW 40 - 120 s

+
R

NH 2 OH minor

Scheme 1.15: Regioselective microwave assisted solvent-free synthesis of -

aminoalcohols79 A more recent method for the aminolysis of epoxides is that reported by Placzek et al.80. This involves the synthesis of -aminoalcohols via a ring opening of epoxides with amines in the presence of a scandium triflate catalyst under solvent-free conditions (Scheme 1.16). The aryl oxiranes underwent cleavage by various amines in a regiospecific fashion with preferential attack at the benzylic carbon. The catalyst could be recycled and reused several times.
O + HN R R' Sc(OTf)3 (5 mol%) solvent-free, RT OH N R R'

Scheme 1.16: Regioselective Sc(OTf)3 catalyzed solvent-free synthesis of -

aminoalcohols80 The synthesis of substituted imidazoles is of importance due to their biological properties. Compounds with the imidazole ring system have many pharmacological properties and play an important role in biochemical processes. One of several ways of synthesizing substituted imidazoles is the four-component condensation of arylglyoxals, primary amines, carboxylic acids and cyanides on Wang resin.81 Balalaie et al.82 have described a novel one-pot, three-component condensation of benzil, benzonitrile derivatives, and primary amines on the surface of silica gel under solvent-free conditions (Scheme 1.17). The reaction was accelerated by microwave irradiation and excellent yields were obtained.

15

Ph Ph O

+
Ph O

Ar

CN

NH2

silica gel MW Ph N R

N Ph

R = Ar, Alkyl

58-92%

Scheme 1.17: Solvent-free synthesis of tetrasubstituted imidazoles on silica gel

support82 In a recent report, Karimi et al.83 have described another facile method for the synthesis of tetrasubstituted imidazoles with a silica gel-supported sodium bisulfate as a catalyst and without any solvent. The reaction involved a four-component condensation of benzil or benzoin, an aldehyde, amine and ammonium acetate under microwave irradiation or heating (Scheme 1.18). The method showed superiority over conventional methods in that it gave excellent yields. Another advantage of this method is that the catalyst is inexpensive and it avoids problems associated with catalyst cost, handling, safety and pollution.
H Ph O O

Ph

+
Ph O R

R'

NH2

NH4OAc/NaHSO4-SiO2 MW or

N Ph N R' R

Scheme 1.18: Solvent-free synthesis of tetrasubstituted imidazoles on SiO2/NaHSO4

support83 More recently, Adib et al.84 have developed a novel and facile method for the preparation of 2,4,6-triarylpyridines by reaction of chalcones with ammonium acetate, with heating under solvent-free conditions (Scheme 1.19). Excellent yields of triarylpyridine products were obtained and required simple purification techniques.

16

Ar' O Ar Ar'
NH4OAc, AcOH (cat.) 100 solvent-free, 4 h C,

Ar

N
93-97%

Ar

Scheme 1.19: Solvent-free synthesis of 2,4,6-triarylpyridines84

Spurred by the success with the above reactions Adib et al.85 went further to develop a simple and versatile route for the synthesis of 2,4,6-triarylpyrimidines under solvent-free conditions and microwave irradiation. The synthesis of Schiff bases has generally been carried out under reflux in methanol or ethanol solution. The disadvantage with this method is that more sensitive Schiff bases tend to undergo some degree of decomposition. Recently, Naeimi et al.86 developed a mild and convenient route of the reaction of carbonyl compounds with amines, under solvent-free conditions and in the presence of a catalyst. They also prepared double Schiff bases and obtained low to excellent yields, depending on the amine used (Scheme 1.20). The only significant disadvantage of this method is that the catalyst (P2O5/Al2O3) is moisture sensitive.
R' R O OH R = H, NO 2 R' = H, CH 3 Y = C 6H4 -O-C 6H 4, C6H 4-CH 2-C 6 H 4, C 6H 4-SO 2-C 6H4 Y + H 2N NH 2 P 2O 5/Al2O 3 Solvent-free OH HO R

R' N

Y N

R' R

Scheme 1.20: Solvent-free synthesis of Schiff bases86

1.4 Nitrogen-donor ligand chemistry

P-donor ligands have received a lot of attention in the fields of organometallic chemistry and catalysis.87 It was only in the mid 1990s that special attention was 17

drawn towards N-donor ligands.88 N-donor ligands have a larger range than that of any other atom and their organic chemistry is varied. The best way to classify Ndonor ligands could be based on the hybridisation of the nitrogen atom, i.e., sp3, sp2 and sp. Ligands with sp2-hybridised nitrogen, such as imines and pyridines, have a significant coordination chemistry.87 Examples of some ligands containing sp2hybridised nitrogen atoms are summarized in Figure 1.2.

N N N N H R N N R N N N

Figure 1.2: Some N-donor ligands with sp2-hybridised nitrogen atoms

The comparison of the well-studied phosphorus ligands and the nitrogen ligands can be done by noting the differences in coordination behaviours as well as the properties of the N-donor ligands.87 (i) The coordination bonds formed by N-donor ligands are fairly stronger than those formed by P-donor ligands and the strength of the bonds depends largely on their covalency with potentially significant contribution from the ionic character of the bond itself.87 (ii) (iii) The strength of the M-N bonds will be affected much more by steric effects than that of the corresponding M-P bonds.87 The N-donors are generally not as effective in forming low-spin complexes and consequently form thermodynamically less stable species but more kinetically labile than their low-spin P-donor analogues.87 (iv) N-donor ligands generally show only a limited -back bonding ability, making these ligands less suitable for the stabilization of low oxidation state transition metals. However, sp2-hybridised N-donors such as pyridine, have been known to show some -back bonding effects between the nitrogen heterocycle and the metal centre.89,90

18

(v)

The N-donor ligands exert a very small trans effect in comparison to other ligands used in organometallic chemistry, resulting in a fast rate of substitution reactions.87

(vi)

The observed reactivity of nitrogen donor ligands is generally high, particularly with alkyl complexes of transition metals containing these ligands.87

As it has been mentioned above that N-donor ligands have a larger range than any other atom, therefore, a few examples of N-donor ligand catalyzed reactions will be chosen, particularly those reactions catalyzed by transition metal complexes containing pyridines and Schiff bases (imines). The examples of reactions that will be focused on include the allylic alkylation, olefin polymerization, cross coupling, epoxidation and ring opening metathesis polymerization (ROMP).

1.4.1 Polymerization reactions

Polymerization reactions required that for the catalysts to be more efficient, the following conditions for the catalysts must apply. The catalyst must: (i) (ii) (iii) have high-olefin insertion ability.91 have two available cis-located sites for polymerization.91 Be stable enough under the usual polymerization conditions.91

The polymerization was catalyzed efficiently by titanium complexes containing bis(alkylphenylaminopyridinato) ligands (Figure 1.3(a)-(e)).92 The ligands were prepared by the reaction of 2-chloropyridine and the appropriate alkylaniline hydrochlorides. The catalysts were formed at room temperature on reaction of the ligands with titanium tetrachloride (TiCl4).

19

N Cl R N Ti

N Cl N

R a) R = 2-Et b) R = 3,5-Me c) R = 4-n-Bu d) R = 2-t-Bu e) R = Ph

Figure 1.3: Bis(alkylphenylaminopyridinato) titanium complexes92

The complex Ie (Figure 1.3) exhibited the highest polymerization activity but produced the lowest molecular weight of polyethylene compared to complexes Ia-d. The decrease in polymerization activity for complexes Ia-e was attributed to the electron donating effects of the alkyl substituents. It was also concluded that as the distance between the alkyl substituent and the metal centre increased, the more active was the catalyst.92 A series of new zirconium complexes bearing bis(phenoxyketimine) ligands have been prepared in low to moderate yields (>70%) (Scheme 1.21).93 The effects of the substituents on the imine carbon and on the phenyl ring of the aniline moiety on polymerization activity were investigated. It was found that when R1 is H atom the molecular weight of polyethylene was low (Mw = 12 000) and the activity 1.6 kg PE mmol-1 Zr .h-1 at 20 C. The best results were obtained when the substituent R1 was electron donating and substituent R2 was an electron withdrawing group.

R2 R1 N OH 1) n-BuLi 2) 0.5 ZrCl4 O R1 N

R2 ZrCl2 2

Bu t

Bu t

Bu t

Bu t

Scheme 1.21: Synthesis of bis(phenoxyketimine) zirconium complexes93

Cloete et al.94 have synthesized functionalized pyridinylimine complexes of palladium as precursor catalysts for ethylene polymerization. The nitrogen atom of the imine functionality contained various substituents, ranging from alkyl to aromatic and allylic groups (Figure 1.4, II). 20

R R' N Cl II a: R = allyl b: R = styryl c: R = phenol d: R = phenyl e: R = propyl III R Ar N Cl N Fe Cl N

R R' Ar

N Pd Cl

a: R = Me, R' = H, Ar = Mes b: R = R' = Me, Ar = Mes C: R = CH 2Ph, R' = H, Ar = Mes d: R = R' =CH 2Ph, Ar = Mes e: R = Me, R' = H, Ar = DIPP f: R = R' = Me, Ar = DIPP g: R = R' = H, Ar = Mes Mes = mesityl (2,4,6-trimethylphenyl) DIPP = 2,6-diisopropylphenyl

R1

N N Fe Cln R2 R2 N

R1

X
IV R 1 , R 2 = H, Me X = Br, I

Figure 1.4: Pyridyl-imine complexes of iron (Fe) and palladium (Pd).94,97,98

The palladium complex IIc exhibited the highest activity at Al:Pd of 2000:1 and whilst complexes IIb reached the optimal activity at Al:Pd of 1500:1. The reason complex
IIc required a higher amount of methylalumoxane (MAO) was due the fact that the

hydroxyl group on the aromatic ring reacted with MAO to form an Al phenoxide adduct.94 The iron-based bis(imino)pyridine complexes have been prepared95-98 and have been used as catalysts for olefin polymerization.97,98 Upon treatment with MAO, all complexes became active in the polymerization of ethylene. Complexes that contained the 2,4,6-trimethylphenyl (Figure 1.4, IIIa-d and IIIg) attached to the imine nitrogen atom were more productive than those that contained the 2,6diisopropylphenyl (Figure 1.4, IIe and IIf). This effect was attributed to less congested active sites for 2,4,6-trimethylphenyl derivatives resulting in higher propagation rates.97 The replacement of the ethyl group in IIe with the isopropyl group to form IIf led to increased polymer molecular weights [Mw 26 000 (IIe), Mw 263 000 (IIf)]. 21

The influence of the para-substituent in bis(arylimino)pyridine iron complexes on the catalytic oligomerization and polymerization of ethylene was investigated.98 These complexes contained phenyl rings bearing halogen (Br, I) substituents at parapositions (Figure 1.4, IV). The complexes where R1 was a methyl group, R2 a hydrogen and bearing a strongly electron withdrawing group at para-position were found to have the highest activities in oligomerization. On the other hand, those complexes where R1 and R2 were methyl groups and bearing a halogen at a paraposition were highly active in polymerization. The extremely high polymerization activities of 4-halo-2-methyl substituted complexes was due to the electronic influence of the halogen at the para-position.98 The Fe(III) analogues of these complexes show more enhanced activities due to increased Lewis acid strength and therefore the coordination of an ethylene molecule is facilitated.98

1.4.2 Cross-coupling reactions 1.4.2.1 Heck reactions

Two pyridine bridged dicarbene palladium(II) complexes (Figure 1.5, V) that were efficient for the Heck coupling reaction have been reported by Nielsen and coworkers.99 These complexes were prepared via a dinuclear silver(I) complex, which was synthesized from the reaction of the tridentate 2.6-bis[(3-methylimidazolium-1yl)methyl] pyridine dibromide and silver(I) oxide in dichloromethane or N,Ndimethylsulfoxide. The compound V (X = Cl) exhibited a higher activity towards the coupling reaction of n-butyl acrylate and 4-bromoacetophenone when treated with hydrazine hydrate, in the absence of the quaternary ammonium salt.99 The main product of the coupling reaction was the expected n-butyl-(E)-4-acetylcinnamate, without any detection of the Z isomer by 1H NMR and gas chromatography.99

22

O N N Pd N X N O Cl Cl X = Cl, Br V VI N

BF 4

Si(CH 2)3 N

Pd

R1 N Pd Cl VII Cl N R2 N Pd E VIII

R1 N R2 R 1 = H, R 2 = i-Pr R 1 = Me, R 2 = i-Pr R 1 = H, R 2 = t-Bu E = CO 2Me

Figure 1.5: Examples of Pd-pyridyl complexes used for the Heck reactions99

Horniakova et al.100 have reported on pyridylimine palladium(II) complex immobilized on a mesoporous silica (Figure 1.5, VI). This complex is heterogeneous in nature and could be used as an alternative to the homogeneous catalysts for the Heck reaction as well as the Suzuki reaction.100 The activity of this complex was compared with quiniline-imine palladium(II) complex. Both catalysts were found to be highly active in the Heck reaction with 100% conversions of the arylhalides and high selectivity towards the E isomer was also observed. Palladium(II) (Figure 1.5, VII) and palladium(0) (Figure 1.5, VIII) complexes based on pyridyl-imine ligands have been synthesized and used as catalyst precursors for the Heck reaction.101 As expected all the ligands were active and promoted the complete conversion of iodobenzene into trans-methyl cinnamate (Z isomer). For the same ligand, the palladium(II) complexes were more active than their palladium(0) analogues.101 Although not mentioned in some articles,99,102 it was apparent that leaching of palladium was a major problem for the homogeneously-catalyzed Heck reactions.101,103

23

1.4.2.2 Suzuki cross-coupling reactions

A range of nickel(0) complexes (Figure 1.6) that contain pyridine, 2,2-bipyridine, 2(2-oxazolyl)pyridine and 2,2-bisoxazole ligands have been prepared and their catalytic activity towards cross-coupling of aryl chlorides by intramolecularly stabilized dialkylaluminium reagents has been studied.104
O N Ni N N N O IX X N N Ni N N

O N Ni N O XI

O N

N Ni N

N N

N O

XII

Figure 1.6: Examples of Ni(0) complexes used for cross-coupling of arylchlorides104

Complexes IX and X exhibited an increase in activity in the presence of THF as a solvent, which enhanced the homo-coupling problem.104 It was also observed that IX and X efficiently catalyzed the cross-coupling of chloroarenes without hydrodehyalogenation occurring. Some silica-supported imine palladacycles have been reported by Bedford and coworkers.105 The objective was to study their catalytic activity as potential heterogeneous catalysts for the Suzuki cross-coupling reaction, and their recyclability was also tested. The synthesis of silica-supported imine palladacycles is illustrated in Scheme 1.22.

24

Br

NR H 2 N(CH 2)3 Si(OEt)3 EtOH, molecular sieves

Br

OHC

R = (CH 2)3 Si(OEt)3

Pd(dba)2, toluene 60C

Br RN Pd PPh 3 PPh 3, CH 2 Cl2 RN

Br Pd 2

R = (CH 2 )3Si(OEt) 3 XIV

R = (CH 2 )3 Si(OEt)3 XIII

Si Si Si HO OHOH Si Br N Pd PPh 3 PPh 3 , CH 2Cl2

Si Si Si HO OHOH Si

silica, toluene reflux temperature

Br N Pd 2

XVI

XV

Scheme 1.12: Synthesis of silica-supported imine palladacycles.105

The silica-supported palladium complexes were very poor in terms of their catalytic activity towards the Suzuki coupling reaction.105 In addition, the complexes were easily recycled but the activity deteriorated in the subsequent reactions. The deterioration in activity was due to the degradation of the catalysts since deep redbrown palladium nanoparticles, which subsequently decomposed to palladium black, were observed.105

25

S Cl R N N Pd Cl S R = Ph XVII R R

S Cl N N Pd Cl S R = Mes = n-Pr = (S)-MeCHPh R

XVIII

Figure 1.7: Palladium imine and amine complexes for coupling of aryl bromides.106

Wiedermann et al.106 have synthesized palladium imine and amine complexes (Figure 1.7) and investigated their activity towards the Suzuki cross-coupling of aryl bromides with phenylboronic acid (Scheme 1.23).
B(OH) 2

Br

+
R

catalyst, 2 eq. Cs 2 CO 3 dioxane R

Scheme 1.23: Suzuki cross-coupling of aryl bromides with phenylboronic acid.106

Complex XVIII (R = Mes) showed a higher catalytic activity than all the other complexes.106 The bulkier mesityl group was responsible for rendering the catalyst more active.106

1.4.3: Epoxidation reactions

A 2-(phenylazo)pyridine rhuthenium(II) complex has been synthesized by Barf and co-workers.107 and their catalytic activity in the epoxidation of stilbene was investigated. Barf and co-workers were able to isolate three isomers, namely transtrans-trans (), trans-cis-cis () and cis-cis-cis () (Figure 1.8).

26

N b

N N

2-(phenylazo)pyridine (pap)

Na Nb Ru Nb Na (t c c) Cl Na Cl Nb

Na Cl Ru Cl Nb (c c c) Na Nb

Cl Na Ru Nb Cl (t t t)

Figure 1.8: Three isomers of Ru(pap)2Cl2107

The two isomers of Ru(pap)2Cl2, and resulted in 100% conversion of stilbene with good selectivity.107 The -isomer which was the most stable gave both lower conversion and selectivity. This was attributed to the steric hinderance of the isomer as was evidenced by the X-ray crystal structure.107 Another interesting example was the use, by Moutet and Ourari,108 of Mn(III) Schiffbase complexes for the electrocatalytic epoxidation and oxidation of cyclooctene. The complexes are shown in Figure 1.9 below. The activity of the catalysts was dependent on the bridging group Z, i.e., the activity decreased from Salen to Salch to Sal(Cl)2ophen complexes. The effect was due to the decrease in stability of the ligand as a result of the increased rigidity.108 The best results for epoxidation of cyclooctene were obtained when salen complex and 2-methylimidazole were used. Recently, Bruno et al.109 have reported on dioxomolybdenum(IV) complexes bearing a bidentate and tetradentate salen-type ligands, that were similar to those prepared by Barf et al.107

27

N R1 R2 O

Z Mn

N O R1 R2 R1 = R2 = H R 1 =Cl, R = H R 1 = R 2 = Cl R 1 = OCH 3, R 2 = H R 1 = NO 2, R 2 = H

Cl

Salen

Salchx

Salophen

Sal(Cl) 2ophen Cl Cl

Z = (CH 2 )2

Z=

Z=

Z=

Figure 1.9: Mn(III) Schiff-base complexes for electrocatalytic epoxidation of

olefins108 An octahedral titanium binaphthyl-bridged Schiff-base complex110 has been prepared and used as a catalyst for the regio- and stereoselective epoxidation of allylic alcohols, under microwave-mediated solvent-free conditions. The cis- isomer was the preferentially formed product according to the X-ray crystal structure (Figure 1.10).110

Cl N N O Cl Bu t N N = N cis- isomer N

Ti O

Figure 1.10: The cis- isomer of the binaphthyl-bridged Schiff base titanium

complex110 The epoxyalcohols could be obtained with very high regio- and chemoselective way by the microwave irradiation of the mixture under solvent-free conditions. Furthermore, high diastereoselectivity could be observed for secondary allylic alcohols.110

28

1.4.4 Asymmetric allylic substitution reactions

Palladium complexes based on the chiral pyridine ligands have been reported111,112 and their catalytic activity in asymmetric allylic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate has been studied. The catalysts were prepared in situ by a reaction of allylpalladium chloride dimer [Pd(3-C3H5)Cl]2 with the ligands 2,2-bipyridines, 2,2,2-terpyridines and 1,10-phenanthrolines (Scheme 1.24).111
OCOCH 3 Ph Ph

CH 2 (CO 2 CH 3 )2 [Pd( -C 3 H 5 )Cl]2 / ligand

3

CH(CO 2 CH 3 )2 Ph

Ph

Scheme 1.24: Allylic alkylation of 1,3-di[henyl-2-enyl acetate with dimethyl

malonate111,112 Phenanthroline catalysts were the most active and their enanioselectivity depended on the distance of the chiral substituent from the heterocyclic nitrogen. On the other hand, the enantioselectivity of bipyridines increased when there was a bulky substituent at the 6-position.111 A series of chiral bidentate ligands containing thiazolyl and pyridyl donors have been synthesized and used for in situ preparation of copper(I) complexes.113 The subsequent copper(I) thiazolyl-pyridine complexes were used for the enantioselective allylic oxidation of cyclohexene with t-butyl perbenzoate. Examples of the chiral bidentate thiazolyl-pyridyl ligands are shown in Figure 1.11. Complexes
XX gave the highest yields of the product, but with low enantioselectivity, while

complexes XXI exhibited higher enantioselectivity. The reason for the higher enantioselectivity of the latter complexes was attributed to steric hindrance at the 8position of the tetrahydroquinoline ring and the thiazole ring. Ligands with a substituent at the 8-position of tetrahydrquinoline led to the (R)-configuration and others led to (S)-configurations.113

29

S N N R XIX R = H, CH 3

S N N R XX R = H, n-Pr, CH 2Ph, CH 2SiMe 3

R2

S N N R1 XXI

R1 = R2 = H R 1 = CH 3, R 2 = H R 1 = i-Pr, R 2 = H R 1 = H 2 = n-Pr R 1 = R 2 = n-Bu R 1 = R 2 = CH 2Ph R 1 = R 2 = CH 2SiMe 3

Figure 1.11: Examples of chiral bidentate thiazolyl-pyridine ligands113

The chiral diimine palladium(II) complexes (Figure 1.12) have been prepared for asymmetric alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate by Albano et al.114

S S N Pd N S R BF 4

Figure 1.12: Chiral diimine palladium(II) catalyst for asymmetric alkylation114

These complexes were less active than their diamine analogues due to the steric hindrance that prevents nucleophilic attack and the electronic issues taking part during the overall oxidative-reductive catalytic cycles.114

1.4.5 Ring-opening metathesis polymerization (ROMP)

Matos et al115 have prepared complexes of the type [RuCl2(PPh3)2L2], where L = pyridine, 4-methylpyridine (picoline), 4-aminopyridine and isonicotinamide. The

30

complexes were investigated for catalytic activity in ring-opening metathesis polymerization. The reaction pathway of ROMP is illustrated in Figure 1.13.
M CHR M CHR M C C C C C C M

C n

CHR

Figure 1.13: The reaction pathway of ROMP116

All catalysts were active only in the presence of ethyldiazoacetate (EDA). Isonicotinamide and aminopyridine gave unimodal polymers with highest molecular weights Mw, but with slightly lower polydispersity indices Mw/Mn. Pyridine and picoline gave bimodal polymers.115 Schiff base substituted first and second generation Grubbs catalysts have described for the polymerization of cyclooctadiene.117 These catalysts showed greater stability and activity than their parent first generation Schiff base catalysts at high temperature but much lower activity than their parent second generation Grubbs catalyst.117 Wright et al.118 have prepared two catalysts that were derivatives of the first generation Grubbs catalyst. Preparation of the catalysts is illustrated in Scheme 1.25. Complex XXIII was prepared via in situ formation of the ligand (Scheme 1.25b).

31

(a) P(i-Pr)3 Cl Ru Cl P(i-Pr)3 Ph + Ar N N N N toluene, RT N Ar 68% N Cl N N N Cl Ru Ph N Ar Ar

XXII (b)

KHMDS N N N N Ar THF

N + P(i-Pr) 3 Cl Ru

Ar

N N Cl N XXIII

N Cl Ru N

Ar Ph THF Ar

Cl P(i-Pr)3

Ph

Petrol

Scheme 1.25: Synthesis of Ru complexes derived from 1st generation Grubbs

catalyst.118 Complex XXII exhibited lower activity than the first and second generation catalyst due to limtations of C-N-C ligand design, particularly on late 4d and 5d transition metals.118 The limitations originated from low lability of metal-nitrogen heterocyclic bonds and the blocking of 3d coordination sites by rigid ligands.118 Catalytic studies of XXIII were hampered by very low yields, coupled with the difficulties to obtain the free carbene.

1.5 Ferrocenyl-nitrogen donor ligand chemistry

1.5.1 Ferrocenyl-pyridine ligands

Despite the extensive work on the symmetrical ferrocenylphosphine119 and unsymmetrical ferrocenyl ligands,120 it was apparent from reviewing the literature that the chemistry of ferrocenyl-nitogen donor ligands, particularly those containing pyridine, has not been well developed. One of the first ferrocenylpyridine complexes was described by Miller et al.121 (Figure1.14a). Electrochemical properties of the 32

complexes were investigated to determine whether the changes in the oxidation state of redox ferrocenyl ligand could lead to changes in the reactivity of the rhenium centre.

Fe Fe
N Cl CO Re N CO CO N Pt N Cl Cl

Fe Fe
(a) (b)

Figure 1.14: Re and Pt complexes with ferrocenylpyridine ligands121,122

A platinum complex has been prepared, that contain 3-ferrocenylpyridine and the specific role of platinum as a linker between the ferrocenyl groups has been studied (Figure 1.14b).122 A single redox wave was observed, corresponding to a two electron oxidation at the platinum electrode indicating little or no communication between the ferrocene groups. Sakanishi et al.123 have reported complexes containing ferrocenylpyridine ligands attached to a tungsten metal centre (Figure 1.15).
R

X
Fe N W(CO)5 Fe N W(CO)4

R = H, Me, Ph

X = CH, N

W(CO)5 N R Fe O 2 R = H, Me N W(CO)5

Fe

Figure 1.15: Tungsten complexes with ferrocenylpyridine ligands123

33

The spectroscopic and electrochemical studies showed that these complexes have architectural and electronic properties necessary to exhibit second-order non-linear optical behaviour. Some complexes that were characterised by X-ray methods crystallized in a centrosymmetric space group and thus could not show second-order non-linear optical properties in the bulk state.123 Braga et al.38,39,124 have described the preparation of supramolecular organometallic materials and coordination networks based on 1,1-bis(4-pyridyl)ferrocene. Example of these ligands are shown in Figure 1.16.
N Fe N N N N

N Fe

N Fe N N

Figure1.16: Examples of ferrocenylpyridyl and pyrimidyl complexes38,39,124

The platinum and palladium complexes of 1,1-bis(2-pyridyl)ferrocene have been prepared and their catalytic reactivity towards carbonyl insertion reactions has been investigated (Figure 1.17).125
Cl Pt Cl N Fe N Pd Cl Me Fe N

N Cl

Cl Pt

Figure 1.17: Pd and Pt complexes of 1,1-bis(2-pyridyl)ferrocene125

A rapid insertion of carbon monoxide into the palladium-methyl bond was observed. However, detailed kinetic studies on the reaction were impossible because of weak ligand-metal bonding. 34

Rajput et al.126 have prepared some palladium(II), platinum(II), rhodium(I) and iridium(I) complexes. Cytotoxicity studies were carried out on selected complexes and these were also screened for activity against oesophageal and cervical cancer cell lines. Complexes with a significant activity in an initial screening assay, and which were soluble in the culture media were further tested to determine their IC50 values. These were compared to IC50 values of cisplatin, determined in the same way and for the same cell line. Interestingly, some of the complexes displayed similar growth inhibitory activity to that displayed by cisplatin. In a more recent publication, Rajput et al
127

have reported on the electrochemical properties of the

rhodium(I) complexes. Results obtained showed some communication between metal centres or a lack of communication in the complexes. A series of pyridyl- and quinolyl-N-substituted ferrocenyl and ferrocenediyl ligands have been synthesized by Gibson and co-workers.128 The activity of the ligands in olefin polymerization was tested after coordination to palladium and nickel metal centres. Examples of the palladium and nickel complexes are depicted in Figure 1.18.

Fe

N X X N

N Y Y N

R R Fe

N X X N

N Y Y N

M = Pd or Ni R = H, Me X = Y = Cl, Br

M = Pd or Ni X = Y = Cl, Br

N Fe X

N Y R Fe N X N Y

M = Pd or Ni R = H, Me X = Y = Cl, Br

M = Pd or Ni X = Y = Cl, Br

Figure 1.18: Palladium and nickel complexes128

The palladium complexes were found to be inactive, but with the nickel-based complexes, although no high molecular weight polyethylene was formed.128 The nickel complexes were highly selective for the formation of short chain oligomers. 35

1.5.2 Ferrocenyl-Schiff base ligands

Recently, there has been an upsurge of interest in preparing ferrocenyl-nitrogen donor ligands based on Schiff bases.124 These are very interesting compounds since the presence
129,130

of

the

ferrocenyl

moiety
130

imparts

special

electrochemical

properties

and modes of coordination.

Some of the ferrocenyl-Schiff base

ligands have been studied for second-order non-linear properties.131 Several research groups have reported on the preparation of cyclopalladated complexes based on ferrocenylimines132-138 and these complexes have been known to catalyse cross-coupling reactions, namely Heck and Suzuki reactions. An example is the dimeric complex prepared by Wu et al.139. The palladium centre is stabilized by a five-membered ring that incorporates the C=N bond (Figure 1.19). Triethylamine and 1,4-dioxane were found to be the suitable base and solvent, respectively. The catalysts were highly efficient for the olefination of iodobenzene and resulted in highly regioselective products (trans-isomers).
CH 3 N Pd X 2 X = Cl, Br CH 3

Fe

Figure 1.19: Dimeric cyclopalladated ferrocenylimine complex for catalytic Heck

reaction139 Zhao et al140 have also reported on the catalytic activity of a cyclopalladated ferrocenylimine complex in the Mizoroki-Heck reaction for the arylation of iodobenzene (Figure 1.20). In this complex the ring is formed by nucleophilic attack of the palladium by the carbon on the second Cp ring and does not incorporate the C=N bond. The complex was highly active and showed high regioselectivity for transcoupling.

36

Fe Pd Ph 3P

N S Cl

Figure

1.20:

Monomeric reaction
140

cyclopalladated

ferrocenylimine

for

Mirozoki-Heck

Weng et al.141 have described the preparation of a 1,1-N-substituted ferrocenediyl palladium(II) complex for the catalysis of Suzuki cross-coupling reaction of aryl iodides bromides with aryl boronic acids, under non-homogeneous conditions in aqueous medium (Figure 1.21). The catalyst exhibited a high activity in the coupling of 4-bromoacetophenone and phenylboronic acid. The catalyst could be easily recovered, recycled and could be used over a number of runs without loss of activity.

N Fe N Pd

Cl Cl

Figure 1.21: 1,1-N-substituted ferrocenediyl Pd(II) complex for Suzuki cross-

coupling reaction141 Zhang et al142 have reported on the synthesis and catalytic activity of the cyclopalladated ferrocenylketimine complexes for the Suzuki cross-coupling reaction, under ultrasonic irradiation in aqueous medium (Figure 1.22). Compared to conventional heating, the reaction occurred faster when accelerated by ultrasonic irradiation although the yields were comparable. Gong et al.143,144 have reported on the catalytic activity of mono-and dimeric cyclopalladated ferrocenylimine complexes for the Suzuki cross-coupling reaction143 and the Buchwald-Hartwig coupling of amines with aryl halides or sulfonates.144

37

CH 3 N Fe Pd X 2 R = X = Cl R = Me, X = I R

Figure 1.22: Dimeric cyclopalladated ferrocenylketimine complexes for Suzuki

reaction143,144 Chiral ferrocenylphosphine-imine ligands containing a pyridine unit have been reported by Hu et al.145 On coordination to a palladium metal centre, highly active catalysts for the asymmetric allylic alkylations. Of particular interest was the influence of the position of the pyridine nitrogen atom on the reactivity and enantioselectivity. The presence of a pyridine unit significantly affected the way a ligand coordinated to the metal centre, which in turn led to dramatic changes in the reactivity and enantioselectivity of the catalytic reaction.145 The ligand with a 3pyridine nitrogen atom (Figure 1.23) resulted in increased reactivity and enantioselectivity, while the ligand with a 2-pyridine nitrogen atom gave no alkylation product.

N PPh 2 Fe

(S,S p)

Figure 1.23: Chiral ferrocenylphosphine-imine ligand145

Other examples of allylic alkylations catalysts are those prepared by Platero-Prats et al.146 These compounds were synthesized by treatment of a ferrocenylimine with an appropriate chloro-bridged dimeric palladium(II)-allyl complex in dichloromethane solution at 25 C. The complexes were active in the allylic alkylation of (E)-3-phenyl2-propenyl nucleophile. 38 (cinnamyl) acetate with sodium diethyl-2-methylmalonate as a

N-ferrocenyl salicylaldimine ligands have been synthesized by Bott et al.147 (Scheme 1.26). After coordination to magnesium, titanium and zirconium metal centres, their catalytic activity in polymerization of olefins was investigated. It was found that on activation with methylalumnoxane (MAO), the titanium complex showed moderate activity for ethylene polymerization, while the zirconium complex was highly active for ethylene oligomerization.

OH NH 2 Fe + OHC Bu t EtOH -H 2O N Fe HO Bu t

Scheme 1.26: Synthesis of N-ferrocene salicylaldimine ligand147

Several groups have reported on the synthesis of bisferrocenylimines from ferrocenecarboxaldehyde148-151 or 1,1-diformylferrocene149,151,152 a range of amines or anilines. Lee et al153 have synthesized cationic rhodium(I) and iridium(I) complexes based on bisferrocenylimine for polymerization of phenylacetylene (Figure 1.24).

N CH Fe

(CH 2) M

N CH Fe ClO 4

M = Rh, Ir

Figure 1.24: Cationic rhodium(I) and Ir(I) complex for olefin polymerization153

Compared to its iridium(I) analogue, the rhodium(I) complex gave high molecular weight polymers in excellent yields while the iridium(I) complex gave better polydispersity indices.

39

1.6 Objectives of the project

The elimination of the hazardous materials in synthetic processes is important especially in the chemical industry and in academia. The versatility of the solventfree approach to organic synthesis has been extensively illustrated with examples in the previous sections. This project focuses on developing a synthetic procedure that reduces or eliminates the use of organic solvents using the green chemistry principles. The main objective of the project is to prepare nitrogen-donor ligands based on ferrocene that can be used in catalysis. Our group42 has previously reported on successful preparation of ferrocenylimines under the solvent-free environment. We intend taking this work a step further and prepare bisferroceylimines ligands for olefin polymerization. The ligands will then be coordinated to a rhodium(I) metal centre. Lee et al.153 have demonstrated that rhodium(I) complexes containing bisferrocenylimines are very effective catalysts for olefin polymerization (Figure 1.24). Based on the work of Lee et al.153 we will investigate the effect of increasing the alkyl chain length on the catalytic activity of the complexes. Rhodium(I) complexes containing diamine ligands have been found to be effective in hydroformylation reactions. Kim and Alper154 have demonstrated that these complexes are effective for hydroformylation reactions (Figure 1.25).

N Rh

Cl Rh

Cl

Figure 1.25: Cationic rhodium(I) complexes for hydroformylation reactions.154

We intend to prepare similar complexes with bisferrocenylamine ligands and investigate their catalytic ligands activity will towards be hydroformylation by simple reactions. reduction The of 40 bisferrocenylamine obtained

bisferrocenylimines, which proceeds much cleaner than the lithium aluminium hydride route.

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118.

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119. 120. 121. 122. 123. 124. 125.

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126. 127. 128. 129. 130. 131. 132. 133. 134. 135.

J. Raput, J. R. Moss, A. T. Hutton, D. T. Hendricks, C. E. Arendse and C. Imrie, J. Organomet. Chem., 689 (2004) 1553. J. Rajput, A. T. Hutton, J. R. Moss, H. Su and C. Imrie, J. Organomet. Chem., 691 (2006) 4573. V. C. Gibson, C. M. Halliwell, N. J. Long, P. J. Oxford, A. M. Smith, A. J. P. White and D. J. Williams, Dalton Trans., 2003, 918. R. Bosque, C. Lpez and J. Sales, Inorg. Chim. Acta, 244 (1996) 141. S. Prez, C. Lpez, A. Caubet, X. Solans, M. Font-Bardia, M. Gich and E. Molins, J. Organomet. Chem., 692 (2007) 2402. C. Imrie, C. Loubser, P. Engelbrecht, C. W. McCleland and Y Zheng, J. Organomet. Chem., 665 (2003) 48. S.-Q. Huo, Y.-J. Wu, C.-X. Du, Y. Zhu, H.-Z. Yuan and X.-A. Mao, J. Organomet. Chem., 483 (1994) 139. R. Bosque, C. Lpez and J. Sales, J. Organomet. Chem., 498 (1995) 147. G. Zhao, Q.-G. Wang and T. W. C. Mak, Polyhedron, 17 (1998) 1. C. Lpez, A. Caubet, S. Prez, X. Solans and M. Font-Bardia, J. Organomet. Chem., 651 (2002), 105.

47

136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146.

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147. 148. 149. 150. 151. 152.

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153. 154.

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49

CHAPTER 2
RESULTS AND DISCUSSIONS

2.1 Solvent-free synthesis of bisferrocenylimines

2.1.1 Introduction

There has been an upsurge of interest in performing chemical transformations under solvent-free conditions. In comparison to methods that employ solvents, the solventfree approach proceeds more cleanly and provides higher yields. Examples of the solvent-free method have been highlighted in the previous chapter. In the literature, Nyamori et al.1 have reported on the solvent-free synthesis of ferrocenylimines by grinding ferrocenecarboxaldehyde and a substituted aromatic amine. This procedure provided excellent yields and the reactions occurred readily at room temperature. However, the reactions in which the aromatic amine contained an electronwithdrawing substituent were slow and thus required heating at 50 C.

O Y Fe C H H 2N X Grind Solvent-free Fe Y

N C X H

Y = Ph, Ph-Ph, Ph-O-Ph

Scheme 2.1: Solvent-free synthesis of ferrocenylimines

The objective of this research was to extend the work and synthesize bisferrocenylimines diamines. (Figure 2.1), by reacting ferrocenecarboxaldehyde with

50

N CH Fe

(CH 2 )

N CH Fe

Figure 2.1: General structure of bisferrocenylimines to be synthesized

The

synthesis

of

bisferrocenylimines

by

reaction

of

diamines

and

ferrocenecarboxaldehyde has been reported by several research groups.2,3 The imines are useful ligands for metal complexation and many ferrocenylimines have been investigated for non-linear optical properties.4

2.1.2 Synthesis and characterization of bisferrocenyimines

The reaction of ferrocenecarboxaldehyde and the appropriate diamines gave the corresponding bisferrocenylimines in excellent yields (Scheme 2.2).

CHO

N H 2N(CH 2 )xNH 2 Grind Fe CH

(CH 2)

N CH Fe

Fe

x = 2, 3, 4, 6, 8

Scheme 2.2: Solvent-free synthesis of bisferrocenylimines

The solvent-free reaction involved the mixing and grinding of two mole equivalents of ferrocenecarboxaldehyde and the appropriate diamine. A pictorial description of the process is shown by a reaction of ferrocenecarboxaldehyde and 1,8-diaminooctane in Figure 2.2. On grinding the mixture of reagents, a melt was obtained which eventually solidified at room temperature, to give the bisimines in excellent isolated yields (Table 2.1). However, for [2.2] the melt obtained only gradually solidified at room temperature, after removal of water formed in the condensation reaction under vacuum.

51

(A) Ferrocenecarboxaldehyde (brown)

1,8-Diaminooctane (white)

(B)

Ground mixture of ferrocenecarboxaldehyde and 1,8-diaminooctane

MELT

(C) Solidified N,Noctylenebis(ferrocenylmethylidine)amine

PRODUCT
Figure 2.2:

The pictorial stages

of

the solvent-free synthesis

of

N,N-

octylenebis(ferrocenylmethylidine)amine

52

Table 2.1: Yields of bisferrocenylimines from the solvent-free reaction of diamines

and ferrocenecarboxaldehyde

FerroceneCompound number carboxaldehyde (Fc-Y-CHO) Diamine

H2N(CH2)xNH2

Yield of Bisferrocenyliminea (%)

N CH Fe (CH 2 ) 2 N CH Fe

[2.1]

FcCHO

H2N(CH2)2NH2 (99%)
N CH Fe (CH 2 ) 3 N CH Fe

[2.2]

FcCHO

H2N(CH2)3NH2 (94%)
N CH Fe (CH 2 ) 4 N CH Fe

[2.3]

FcCHO

H2N(CH2)4NH2 (92%)
N CH Fe (CH 2 ) 6 N CH Fe

[2.4]

FcCHO

H2N(CH2)6NH2 (94%)
N CH Fe (CH 2 ) 8 N CH Fe

[2.5]

FcCHO

H2N(CH2)8NH2 (97%)
CH
Fe

N CH
Fe

[2.6]

Fc

CHO

H2N(CH2)2NH2 (97%)

The isolated yields are based on starting materials.

53

The solidified melt was initially analyzed by infrared (IR) spectroscopy using a potassium bromide (KBr) disc, in order to determine that the reaction occurred under solvent-free conditions. Infrared analysis showed the disappearance of the carbonyl (C=O) band at approximately 1700 cm-1 and the appearance of the strong imine (C=N) band at 1646 cm-1. Figure 2.3 shows the IR spectrum of [2.5] immediately after the melt had solidified. The absence of the carbonyl band in the IR spectrum was evidence that the reaction was completed under solvent-free conditions.

Figure 2.3: IR spectrum of [2.5]

The solidified melt was ultimately recrystallized from a minimal amount of cold anhydrous methanol to provide a pure product.
1

H NMR spectra of all the

bisferrocenylimines [2.1]-[2.6] showed proton signals in the region 8.1-8.2 ppm which were indicative of the presence of imine (CH=N) protons. Compounds [2.1]2 and [2.6]5 have been synthesized previously; however, they are reported here for the first time under solvent-free conditions. 1H NMR spectra of [2.1]-[2.5] were expected to possess some similarities since the only difference in their molecular structures was the length of the alkyl chain of the diamines. A singlet was observed at 3.78 ppm for [2.1], indicatve of the four protons for the two (CH2) groups. Compound [2.2] has an additional CH2 group in the -position and exhibited a triplet at 3.56 and a 54

multiplet at 2.03 ppm due to the four protons of the two terminal () CH2 groups and two protons of the middle () CH2 group, respectively. As expected, [2.3] with four CH2 groups exhibited a triplet at 3.7 ppm due to the protons on the terminal () CH2 groups and a multiplet at 1.71 ppm due to the protons on the middle () CH2 groups. Three signals were observed for [2.4], a triplet at 3.45 ppm for the protons on the terminal () CH2 groups and two multiplets at 1.66 and 1.44 ppm for the protons on the inner () CH2 groups and the middle () CH2 groups, respectively. An interesting scenario was observed with [2.5] where instead of four signals that would have been expected, only three were observed. A triplet at 3.42 ppm due to the protons on the terminal () CH2 groups, a multiplet at 1.62 ppm for the inner () CH2 groups and a singlet for the protons on the four middle CH2 groups were observed (Figure 2.4).

Figure 2.3: 1H NMR spectrum of [2.5]

This suggested that the deshielding effect of the nitrogen groups became less pronounced as the length of the alkyl chain increased. The substituted cyclopentadienyl (Cp) ring of the ferrocene moiety for all the compounds was represented by two triplets and a very intense singlet for the unsubstituted cyclopentadienyl ring. For all the compounds [2.1]-[2.5] the chemical shifts of the protons on the carbons directly bonded to the nitrogen groups were expected to be 55

very similar. However, this was not the case and the results are summarized in Table 2.2. This table shows that the proton signals are shifted to lower frequencies (less deshielding) as the length of the alkyl chains increased. This effect could be attributed to the increased free rotation and flexibility of the chain as the length increased. A significant change was observed between [2.1] and [2.2] as well as
[2.2] and [2.3], while there was less change from [2.3] to [2.4] to [2.5]. Additionally,

for [2.2]-[2.5], these protons appeared as triplets, indicating some vicinal protonproton coupling. For [2.1] a singlet was observed showing that there was no vicinal coupling between the neighbouring protons.
Table 2.2: Chemical shifts for protons on the carbon directly bonded to nitrogen

group

Compound

Chemical shift (ppm)

[2.1]

3.78

[2.2]

3.56

[2.3]

3.47

[2.4]

3.45

[2.5]

3.42

13

C NMR spectra for all compounds showed signals, for the imine carbons, in the

region 160-163 ppm. The observed carbon signals for all compounds [2.1]-[2.5] were as expected. Compound [2.1] exhibited a single signal at 62.80 ppm for two CH2 groups while for [2.2] two signals were observed at 59.25 and 32.90 ppm

56

representing the carbons directly bonded to nitrogen groups and the middle carbons, respectively. Compounds [2.3], [2.4] and [2.5] exhibited two, three and four carbon signals, respectively, in the expected chemical shift regions for the CH2 groups. All the compounds are very stable in the solid state at room temperature and in open air while they showed some degree of instability in solution. This was in accordance with findings of Benito et al.2 Attempts to perform the same reaction using acetylferrocene were unsuccessful, even after heating the reaction mixture up to 65 C. The inability of acetylferrocene to react was attributed to steric hindrance by the methyl group.

2.1.3 Solvent-free synthesis of arylbisimines

The synthesis of the arylbisimines in a solvent-free environment has been reported by Naeimi and co-workers.6 The method included the use of a solid-supported catalyst P2O5/Al2O3 (Scheme 2.3).
R' R O OH R = H, NO 2 R' = H, CH 3 Y = C 6H 4 -O-C 6 H 4 , C 6H 4 -CH 2 -C 6 H 4 , C 6H 4 -SO 2 -C 6H 4 Y + H2N NH 2 P 2O 5 /Al2 O 3 Solvent-free OH HO R

R' N

Y N

R' R

Scheme 2.3: Solvent-free synthesis of arylbisimines in the presence of a catalyst.6

Similar types of arylbisimines have been synthesized in this study, where the aromatic ring contained methyl substituents at 2,3-, 2,5- and 2,4,6-positions. The Yspacer was a two-carbon alkyl chain and no catalyst was required. The reactions involved mixing and stirring of two mole equivalents of an appropriate substituted benzaldehyde, and ethylenediamine. Stirring the reagents for a few seconds gave a white solid, an indication that the reaction had taken place since both starting reagents are liquids (Scheme 2.4).

57

R4 R1 R2 O H R5 R4 H 2N stir solvent-free R2
3 6 4

R1
2 1

R5
6'

5'

4' R 3 3'

N
5

1'

2'

R2

NH 2

R3

R3

R5

R1

R4

[2.7]: R 1, R2 = CH 3; R3, R 4, R5 = H [2.8]: R 1, R3 = CH 3; R2, R 4, R5 =H [2.9]: R 1, R 3, R 5 = CH3 ; R 2, R4 =H

Scheme 2.4: Solvent-free synthesis of arylbisimines

Although it was apparent that the reaction took place under these solvent-free conditions, the reaction mixture was analysed by IR spectroscopy using KBr discs to confirm that the reaction had indeed occurred under these conditions. IR analysis showed the disappearance of the carbonyl band at approximately 1700 cm-1 and the appearance of the imine (C=N) band in the region 1637-1639 cm-1. The white crude solid was eventually recrystallized from cold anhydrous methanol to obtain the pure product in excellent yield (Table 2.3). 1H NMR revealed that there was no aldehydic proton signal present in the region 9.7-10 ppm for all the compounds. The major differences between the compounds were expected to be in aromatic region of the spectra and the methyl substituents. Compound [2.7] was identified by the presence of two singlets at 2.33 and 2.27 ppm representing the methyl groups at 2, 2 and 3, 3 positions of the aromatic rings, respectively. For [2.8] two singlets were also observed at 2.39 and 2.29 ppm for the methyl groups at 2, 2 and 5, 5 positions, respectively. Compound [2.9] contained three methyl substituents at 2, 2, 4, 4 and 6, 6 positions. For the aromatic rings, [2.7] exhibited two doublets at 7.69 and 7.20 ppm due to protons at the 6, 6 and 4, 4 positions, respectively, and a triplet at 7.10 ppm due to protons at 5, 5 positions.. A singlet at 7.66 ppm for [2.8] represents the protons at the 6, 6 positions.

58

Table 2.3: Yields of arylbisimines from a reaction of substituted benzaldehyde and

ethylenediamine

Substituted Benzaldehyde Ethylenediamine

Yield of Arylbisiminea (%)

O
H 2N

NH 2

[2.7]
O H

(86%)

H 2N

NH 2

[2.8]
O H
N

(84%)

H 2N

NH 2

[2.9]
a

(88%)

Yields are based on starting materials

Two doublets were also observed at 7.11 and 7.07 ppm for the protons at the 3, 3 and 4, 4 positions, respectively. As anticipated, the 1H NMR for [2.9] showed some chemical shift equivalence of the protons on the aromatic rings as only a singlet at 2.37 ppm was observed.
13

C NMR spectra of all compounds exhibited signals for the

13

C=N group in the region 161-162 ppm. The

C NMR spectra of [2.7] and [2.9]

showed six and four signals for the aromatic rings, respectively, while the spectrum of [2.8] gave rise to five signals. Actually, there were six signals since the signal at

59

131.1 ppm (highlighted) represented two overlapping signals, one lower in intensity. Figure 2.5 illustrates the aromatic region of the 13C NMR spectrum of [2.8].

Figure 2.4: 13C NMR spectrum of [2.8]

According to predicted chemical shifts as implemented in ChemDraw, the signals were assigned to C3, C3 and C4, C4. The signals for the methyl groups were observed at 19.81 and 14.10 ppm for [2.7]. The methyl signals for [2.8] were observed at 20.38 and 18.46 ppm while for [2.9] signals appeared at 21.52 and 21.06 ppm. The signals for the CH2 groups were observed at 62.17, 62.15 and 63.89 ppm for [2.7], [2.8] and [2.9], respectively. Since the major difference between the three compounds was the number and the positions of the methyl groups on the aromatic rings, it seemed as though the more methyl groups there were present, the greater the downfield shift of the CH2 groups.

2.2 Reduction reaction of bisferrocenylimines and arylbisamines

2.2.1 Reduction of bisferrocenylimines

The reduction of bisferrocenylimines with lithium aluminium hydride has been reported elsewhere in the literature.2 Our interest was to carry out this transformation using a much cleaner synthetic route. We therefore opted for the catalytic 60

hydrogenation reaction procedure (Scheme 2.5), which takes place cleanly since the only product is the corresponding bisferrocenylamine.
H N CH Fe H 2, Pd/C MeOH Fe C H2 H N C H2 Fe

N CH Fe

(CH 2)

(CH 2)

x = 2, 3, 4, 6, 8

Scheme 2.5: Hydrogenation of ferrocenylbisimines

However, attempts to carry out the reactions yielded no results. We were then forced to use the lithium aluminium hydride route. The reaction was carried out by heating a solution of the bisferrocenylimine in diethylether for 30 minutes. The reaction was then quenched with ice/water slurry and the product extracted with diethyl lether. The products were obtained in excellent yield as pale to bright yellow solids (Table 2.4). Similar types of compounds that are C2-symmetric have been reported by Woltersdorf et al.7 The 1H NMR spectra of all the reduction products showed the disappearance of the imine proton signal and the appearance of two new signals, the amine (NH) and the CH2 proton signals. For all the compounds
[2.10]-[2.14] the NH proton signal was observed as a broad singlet in the chemical

shift region 1.53-2.27 ppm. The CH2 proton signal on the other hand, was observed as singlet in the chemical shift region 3.52-3.58 ppm. It was also observed that one of the substituted Cp ring proton signals was shifted to lower chemical shifts for all the compounds. The CH2 proton signal in the reduced form of the bisferrocenylimines was observed in the expected chemical shift region. The terminal CH2 proton signals of the alkyl chains appeared to have been shifted to lower frequencies compared to those in the original bisferrocenylimines. In the bisferrocenylimines the terminal CH2 proton signal appeared at higher frequencies largely due to anisotropic effects of the double bond (CH=N). All the terminal CH2 signals were shifted to lower frequencies by ca. 0.8 ppm, which is in agreement with the literature value.8
13

C NMR spectra showed the disappearance of the CH=N

carbon signal and a new CH2 carbon signal, in the expected region, for all the compounds [2.10]-[2.14].

61

Table 2.4: Yields of bisferrocenylimines

Compound
H N Fe C H2 (CH 2 )
2

% Yielda
C H2

H N Fe

87% [2.10]
H N Fe C H2 (CH 2 )
3

H N C H2 Fe

92%

[2.11]
H N Fe C H2 (CH 2 )
4

H N C H2 Fe

86%

[2.12]
H N Fe C H2 (CH 2 )
6

H N C H2 Fe

91%

[2.13]
H N Fe C H2 (CH 2 )
8

H N C H2 Fe

88%

[2.14]
a

Yields are based on starting materials

Infrared spectra of all compounds showed the appearance of several peaks corresponding to the v(NH) stretching vibration which occurred in the region 33003100 cm-1. Furthermore, the v(CH=N) stretching peak which occurs as a strong absorption in the region 1640-1645 cm-1 for the bisferrocenylimines was lacking. The above information was in agreement with the proposed molecular structures of the compounds. 62

2.2.2 Reduction of arylbisimines

The reduction of arylbisimines was carried out using the same method as for the reduction of bisferrocenylimines. These compounds were obtained in moderate to good yield as a white powder, except for [2.15] which was obtained as a colourless oil. However, it was also found that [2.15] solidified to a white solid after prolonged drying process under suction. 1H NMR spectra of all compounds [2.15]-[2.17] showed the disappearance of the CH=N proton signal and the appearance of CH2 and NH protons signals. The peak in the chemical shift region 3.94-3.96 ppm represented the CH2 proton signal for all the compounds. The NH proton signal was obtained as a broad singlet in the region 3.76-3.81 ppm. The signal for the CH2 groups of the ethylene chain in arylbisimines appeared at higher frequencies than those of the arylbisamines largely due to anisotropic effects of the imine double bond. The shift to lower resonance frequencies in the CH2 signals in arylbisamines confirmed the reduction of the CH=N double bond to a CH2-NH single bond. The formation of the arylbisamines was also confirmed by
13

C NMR spectrometry. The

appearance of a new signal in the chemical shift region 48.2-51.77 ppm was due to the presence of the CH2 group. Infrared spectra showed the appearance of several peaks for the (NH) stretching vibration at 3350-3150 cm-1 for all the compounds.

2.3 Electronic Spectroscopy

The UV-visible spectra of bisferrocenylimines and bisferrocenylamines prepared were obtained in dichloromethane solution. Spectral comparisons with unsubstituted ferrocene as a reference were also made. Ferrocene exhibited two bands at wavelengths of max 326 and 442 nm, which have been assigned to 1A2g1E2g and
1

A1g1E1g ligand field d-d transitions.9 The UV-vis spectrum of unsubstituted

ferrocene is illustrated in Figure 2.6.

63

Figure 2.6: UV-vis spectrum of unsubstitued ferrocene in dichloromethane

The ferrocenyl bands in [2.1]-[2.5] were observed at longer wavelengths max (Figure 2.7, Table 2.5) largely due to conjugation with the CH=N bond. Bathochromic shifts (shifts to longer wavelengths) are anticipated where conjugation increases in length. Some absorption bands due to -* and n-* transitions of the imine groups CH=N in [2.1]-[2.5] were also observed at wavelengths lower than 300 nm. The ferrocenyl bands in [2.10]-[2.15] were observed at slightly shorter wavelengths max (Figure 2.8, Table 2.5) largely due to the reduction of the CH=N bond resulting to decrease in conjugation. Shifts to lower wavelengths are termed hypsochromic shifts and are expected where there is a decrease in conjugation length. The extinction coefficients of [2.1]-[2.5] were higher for the band at lower wavelengths and lower for the band at higher wavelengths than that of ferrocene (Table 2.5). On the other hand, for
[2.10]-[2.14], the situation was restored to that of the unsubstituted ferrocene.

64

Figure 2.7: UV-vis spectra of bisferrocenylimines in dichloromethane

Figure 2.8: UV-vis spectra of bisferrocenylamines in dichloromethane

65

Table 2.5: UV-vis data for ferrocene, [2.1]-[2.5] and [2.10]-[2.14] Compound Ferrocene [2.1] [2.2] [2.3] [2.4] [2.5] [2.10] [2.11] [2.12] [2.13] [2.14]
= molar extinction coefficient

max(nm) [(L.mol-1.cm-1)] 326 [202] 329 [2586] 323 [3638] 321 [2934] 323 [3180] 321 [2836] 322 [140] 323 [204] 324 [137] 323 [160] 324 [182] 442 [335] 454 [914] 448 [1087] 450 [852] 448 [910] 445 [803] 438 [177] 469 [219] 437 [208] 438 [230] 439 [245]

2.4 Cyclic Voltammetry

The redox behaviour of bisferrocenylimines and bisferrocenylamines was studied by cyclic voltammetry. The observed redox behaviour of the compounds was compared with that of ferrocene as a standard reference. Ferrocene exhibited a one-electron reversible wave with an E1/2 at 90.5 mV (Figure 2.9). The cyclic voltammograms were recorded in acetonitrile with tetrabutylammonium perchlorate (0.1 M) as a supporting electrolyte, in an inert environment. The three-electrode system was a platinum disk working electrode, a platinum wire auxiliary electrode and Ag/AgNO3 reference electrode. Some typical cyclic voltammograms of selected compounds are shown in Figure 2.10, and show one-electron reversible redox waves similar to that of ferrocene. The bisferrocenylimines exhibited a positive shift in potential indicating that these compounds became more difficult to oxidise (Figure 2.10, Table 2.6). These positive shifts can be attributed to the presence of the CH=N bond in close proximity to the ferrocene group, resulting in the reduced electron density at the metal centre.

66

Figure 2.9: Cyclic voltammogram of ferrocene in acetonitrile

As expected the bisferrocenylamines exhibited a negative shift since the CH2-NH bond had no effect on the metal centre.

Figure 2.10: Cyclic voltammograms of [2.2], [2.5], 2.12] and [2.14]

67

Table 2.6: Half-wave potentials of [2.1]-[2.5] and [2.12]-[2.14]a Compound Ferrocene [2.1] [2.2] [2.3] [2.4] [2.5] [2.12] [2.13] [2.14]
a

Epa (mV)

Epc (mV)

E1/2 (mV)

140 243 246 243 238 242 101 111 112

41 124 167 171 168 163 23 35 25

90.5 133.5 206.5 207 203 202.5 62 73 68.5

Due to solubility problems acceptable voltammograms of compounds [2.6], [2.10] and [2.11] could not be recorded.

2.5 Experimental
2.5.1 Purification procedures

All reagents and solvents were purified using standard purification and drying methods.10
Table 2.7: General drying agents for solvents Solvent Drying Agent

Diethyl ether Methanol Ferrocenecarboxaldehyde, 2,3and

Na wire Mg turnings, I2 2,5-dimethylbenzaldehyde and 2,4,6-

trimethylbenzaldehyde were purchased from the Sigma Aldrich Chemical Company. All other common laboratory chemicals were obtained locally and were used without further purification.

68

2.5.2 Instrumentation

Melting points were determined on an Electrothermal IA 900 series digital melting point apparatus and were uncorrected. NMR spectra were recorded on a Bruker DPX (300 MHz) spectrometer at ambient temperatures. 1H NMR spectra were referenced against the deuterated solvent (CDCl3: 7.28) and the values reported relative to tetramethylsilane (TMS: 0.00).
13

C NMR spectra were similarly referenced internally to the solvent resonance

(CDCl3: 77.0) with values reported relative to tetramethylsilane (TMS: 0.00). Infrared spectra were recorded on a DigiLab FTS 3100 Excalibur HE series, running DigiLab Resolution 4.0 software with solid samples prepared as potassium bromide (KBr) disks. Microanalyses were obtained on a Carlo Erba EA 1108 elemental analyser at the University of Cape Town. Fast atomic bombardment (FAB) and high resolution (EI) mass spectra were recorded on a micromass auto-Tof mass spectrometer at the Witwatersrand University in South Africa. Uv-vis spectra were recorded on a Hewlett Packard 8452A diode array spectrometer in dichloromethane (10-3 M) with a cell width of 1 cm. Cyclic voltammograms were obtained on a BAS 100B electrochemical analyser with a three-electrode system using Ag/AgNO3 (0.01 M) as a reference electrode, platinum wire as the auxiliary electrode and platinum disc as the working electrode. Samples (10-3 M) were prepared and run under nitrogen at ambient temperatures, in acetonitrile with tetrabutylammonium perchlorate (0.1 M) as a background electrolyte. The scan rate used was 100 mV.s-1. Solutions were saturated with nitrogen by bubbling for 10 minutes prior to each run. The system gave ferrocene E1/2 = 90.5 mV.

69

2.6 Synthesis of bisferrocenylimines and arylbisimines

2.6.1 General procedure for the synthesis of bisferrocenylimines

Ferrocenecarboxaldehyde (2 mole equivalents) and the diamine (1 mol equivalent) were added to a pyrex tube fitted with glass ground joint. The two compounds were ground together at room temperature (ca. 25C) using a glass rod The pyrex tube was then placed under a high vacuum pump overnight. The products were obtained as yellow to orange solids after recrystallization from cold anhydrous methanol.
2.6.1.1 N,N-Ethylenebis(ferrocenylmethylidene)imine [2.1]

The general procedure was followed using ferrocenecarboxaldehyde (360 mg, 1.68
CH Fe

(CH2)

N CH Fe

mmol) and ethylenediamine (50 mg, 0.84 mmol). N,N-Ethylenebis(ferrocenylmethylidine)amine was obtained as a yellow solid (380 mg, 99%). M.p. 147-150 1H NMR (CDCl3): 8.18 (2H, s, N=CH), 4.63 (4H, t, C; J = 1.8, C5H4), 4.30 (4H, t, J = 1.8, C5H4), 4.16 (10H, s, C5H5), 3.78 (4H, s, 2 x CH2);
13

C NMR (CDCl3): 162.74, 80.85, 70.75, 69.52, 68.86, 62.80; IR (KBr): 3113, 3071,

2917, 2897, 2832, 1782, 1705, 1643, 1462, 1412, 1381, 1327, 1281, 1246, 1215, 1211, 1103, 1049, 1011, 961, 891, 822, 768, 644, 594, 517, 486, 475, 436, 401; m/z (EI): 453 (29%), 452 ([M+], 80%), 321 (13%), 256 (31%), 241 (22%), 227 (19%) 226 (63%), 213 (92%), 199 (27%), 186 (14%), 160 (14%), 121 (63%), 69 (21%), 56 (16%), 43 (11%), 41(11%), 32 (32%), 30 (11%), 28 (100%); Anal. Calc. for C24H24N2Fe2: MW, 452.15076. Found: MW, 452.063965.
2.6.1.2 N,N-Propylenebis(ferrocenylmethylidene)imine [2.2]

The general procedure was followed using ferrocenecarboxaldehyde (200 mg, 0.93
CH Fe

(CH2)

N CH Fe

mmol) and 1,3-diaminopropane (41 mg, 0.55 mmol). N,N-Propylenebis(ferrocenylmethylidine)amine was obtained as an orange solid (204 mg, 94%). M.p. 127-129 1H NMR (CDCl3) 8.18 (2H, s, N=CH), 4.67 C; (4H, t, J = 1.8, C5H4), 4.39 (4H, t, J = 1.8, C5H4), 4.21 (10H, s, C5H5), 3.56 (4H, t, J = 70

7.0, 2 x CH2), 2.03 (2H, m, CH2);

13

C NMR (CDCl3) 160.57, 81.88, 70.28, 69.25,

68.64, 59.25, 32.90; IR (KBr) 3108, 3066, 2929, 2946, 2866, 2823, 1640, 1470, 1449, 1323, 1243, 1105, 1004, 823, 544; m/z (EI) 467 (24%), 466 ([M+], 100%), 401 (30%), 335 (56%), 255 (55%), 254 (38%), 253 (30%), 241 (24%), 240 (60%), 233 (26%), 227 (62%), 226 (24%), 225 (21%), 212 (36%), 199 (38%), 186 (52%), 129 (25%), 120 (90%), 56 (52%), 39 (28%); Anal. Calc. for C25H26N2Fe2: C, 64.41; H, 5.62; N, 6.01; MW, 466.17734. Found: C, 63.15; H, 5.82; N, 5.75; MW, 466.082825.
2.6.1.3 N,N-Butylenebis(ferrocenylmethylidene)imine [2.3]

The general procedure was followed using ferrocenecarboxaldehyde (200 mg, 0.93
CH Fe

(CH2)

N CH Fe

mmol) and 1,4-diaminobutane (44 mg, 0.50 mmol). N,N-Butylenebis(ferrocenylmethylidine)amine was isolated as an orange solid (207 mg, 92%). M.p. 152-154 1H NMR (CDCl3) 8.19 (2H, s, CH=N), 4.65 C; (2H, t, J = 1.8, C5H4), 4.36 (2H, t, J = 1.7, C5H4), 4.19 (10H, s, C5H5), 3.47 (4H, t, J = 7.0, 2 x CH2), 1.71 (4H, m, 2 x CH2);
13

C NMR (CDCl3) 160.29, 81.08, 70.69, 69.47,

68.78, 62.07, 29.09; IR(KBr) 3071, 2930, 2860, 2814, 2364, 1644, 1470, 1439, 1407, 1381, 1369, 1324, 1244, 1104, 1041, 1020, 1001, 962, 930, 819; m/z (EI) 481 (5%), 480 ([M+], 13%), 284 (15%), 268 (23%), 267 (100%), 213 (15%), 199 (17%), 121 (50%), 56 (18%), 55 (15%), 44 (25%), 43 (34%), 41 (26%), 39 (22%), 30 (67%), 28 (61%), 27 (20%). Anal. Calc.1 for C26H28N2Fe2: C, 65.03; H, 5.88, N, 5.83; MW, 480.20392. Found: C, 64.51; H, 6.05; N, 5.74; MW, 480.095172.
2.6.1.4 N,N-Hexylenebis(ferrocenylmethylidene)imine [2.4]

The general procedure was followed using ferrocenecarboxaldehyde (100 mg, 0.47 mmol) and 1,6-diaminohexane (24 mg, 0.23
CH Fe

(CH 2 )

N CH Fe

mmol). N,N-Hexylenebis(ferrocenylmethylidine)amine was isolated as a light yellow solid (109 mg, 94 %). M.p. 109-111 1H NMR (CDCl3) 8.16 (2H, s, CH=N), 4.65 C; (4H, t, J = 1.8, C5H4), 4.36 (4H, t, J = 1.8, C5H4), 4.19 (10H, s, C5H5), 3.45 (4H, t, J =
The tendency for the C and N content to be too low and H too high could be due to the presence of traces of water. This also applies to compounds [2.4] and [2.5].
1

71

6.2, 2 x CH2), 1.66 (4H, m, 2 x CH2), 1.44 (4H, m, 2 x CH2);

13

C NMR (CDCl3)

161.08, 81.96, 70.67, 69.46, 68.78, 62.30, 31.32, 27.61; IR (KBr) 3099, 2935, 2862, 2822, 1646, 1468, 1454, 1409, 1381, 1351, 1326, 1243, 1204, 1164, 1103, 1063, 1051, 1038, 1004, 957, 936, 876, 865, 846, 826, 807; m/z (EI) 509 (15%), 508 ([M+], 41%), 312 (20%), 296 (19%), 295 (71%), 214 (23%), 213 (26%), 199 (27%), 186 (30%), 121 (100%), 56 (34%), 55 (22%), 43 (24%), 41 (39%), 39 (41%), 30 (27%), 28 (49%), 27 (33%). Anal. Calc. for C28H32N2Fe2: C, 66.17; H, 6.35; N, 5.51; MW, 508.25708. Found: C, 64.31, H, 6.46; H, 5.40; MW, 508.126146.
2.6.1.5 N,N-Octylenebis(ferrocenylmethylidene)imine [2.5]

The general procedure was followed using ferrocenecarboxaldehyde (200 mg, 0.93 mmol) and 1,8-diaminooctane (239mg, 0.47
CH Fe

(CH 2)

N CH Fe

mmol). N,N-Octylenebis(ferrocenylmethylidine)amine was obtained as a yellow solid (231 mg, 97 %). M.p. 97-100 1H NMR (CDCl3) 8.15 (2H, s, N=CH), 4.65 (4H, t, J C; = 1.8, C5H4), 4.36 (4H, t, J = 1.8, C5H4), 4.19 (10H, s, C5H5) 3.42 (4H, t, J = 6.6, 2 x CH2), 1.62 (4H, m, 2 x CH2), 1.40 (8H, s, 4 x CH2);
13

C NMR (CDCl3) 161.00, 81.13,

70.66, 69.46, 68.78, 62.35, 31.33, 29.84, 27.73; IR (KBr) 3065, 2923, 2848, 2819, 1646, 1612, 1494, 1471, 1371, 1327, 1243, 1106, 1043, 1022, 1001, 950, 824, 768, 725, 545; m/z (EI) 537 (29%), 536 ([M+],100%), 471 (20%), 341 (14%), 340 (79%), 268 (19%), 226 (15%), 213 (19%), 199 (26%), 186 (15%), 121 (49%), 55 (16%), 43 (14%), 30 (43%). Anal.Calc. for C30H36N2Fe2: C, 67.19; H, 6.77; N, 5.22; MW, 536.31024. Found: 65.23; H, 7.19; N, 5.59; MW, 536.157307.
2.6.1.6 N,N-Ethylenebis(4-phenylferrocenylmethylidene)imine [2.6]

The general procedure was followed using 4Ferrocenylbenzaldehyde (75 mg, 0.26 mmol) and ethylenediamine (10 mg, 0.15 mmol). N,N-Ethylenebis(4-phenylferrocenylmethylidene)amine was obtained as an orange solid (73 mg, 97 %). M.p 208-210 1H NMR (CDCl3) 8.33 (2H, s, N=CH), 7.63 (4H, C; dd, J = 8.3, C6H4), 7.49 (4H, dd, J = 8.3, C6H4), 4.69 (4H, t, J = 1.8, C5H4), 4.38 (4H, t, J = 1.8, C5H4), 4.06 (10H, s, C5H5), 3.99 (4H, s, 2 x CH2);
13

CH
Fe

N CH
Fe

C NMR (CDCl3) 72

162.99, 128.59, 126.41, 85.01, 70.31, 70.12, 69.81, 67.05; IR (KBr) 3098, 2913, 2847, 2230, 1638, 1605, 1566, 1528, 1454, 1420, 1373, 1362, 1308, 1281, 1227, 1181, 1103, 1084, 1018, 995, 887, 864, 822, 648, 513, 509, 451; m/z (EI) 605 (38%), 604 ([M+, 75%), 302 (17%), 287 (14%), 180 (7%), 152 (9%), 139 (7%), 121 (48%), 69 (10%), 63 (22%), 62 (17%), 56 (38%), 43 (18%), 39 (69%), 38 (28%), 37 (15%), 29 (35%), 28 (100%), 27 (66%), 26 (30%); Anal. Calc. for C36H32N2Fe2: MW, 604.34268. Found: MW, 604.134521.
2.6.1.7 N,N-Bis-(2,3-dimethylbenzylidene)-ethane-1,2-diimine [2.7]

2,3-Dimethylbenzaldehyde (202 mg, 1.5 mmol) and ethylenediamine (45 mg, 0.91 mmol) were added into a 25 cm roundbottomed flask. The two compounds were stirred using a magnetic stirrer at room temperature (ca. 25C). The round bottomed flask was placed under high vacuum overnight. N, N-Bis-(2,3dimethylbenzylidine)-ethane-1,2-diamine was obtained as a white powder (188 mg, 86 %). M.p. 119-121 1H NMR (CDCl3) 8.68 (2H, s, CH=N), 7.69 (2H, d, J = 7.6, C; Ar-H), 7.20 (2H, d, J = 7.2, Ar-H), 7.10 (2H, t, J = 7.6, Ar-H), 3.95 (4H, s, 2 x CH2), 2.33 (6H, s, 2 x CH3), 2.27 (6H, s, 2 x CH3);
13 3

C NMR (CDCl3) 161.62, 137.42,

136.41, 134.99, 131.76, 125.88, 125.67, 62.17, 19.81, 14.10; IR (KBr) 3063, 3005, 2964, 2972, 2907, 1637, 1591, 1458, 1374, 1281, 1261, 1197, 1183, 1092, 1010, 990, 980, 956, 903, 798, 784, 760, 716, 488, 426; m/z (EI) 293 (10%), 292 ([M+], 38%), 291 (35%), 162 (30%), 161 (100%), 160 (65%), 159 (19%), 158 (28%), 147 (20%), 146 (86%), 144 (26%), 134 (15%), 133 (69%), 132 (90%), 131 (48%), 130 (37%), 119 (70%), 118 (22%), 117 (29%), 116 (23%), 115 (19%), 105 (15%), 103 (16%), 91 (39%), 77 (21%), 69 (19%), 57 (18%), 55 (16%), 43 (16%), 41 (20%), 28 (31%). Anal. Calc. for C20H24N2: MW, 292.41796. Found: MW, 292.193095.
2.6.1.8 N,N-Bis-(2,5-dimethylbenzylidene)-ethane-1,2-diimine [2.8]

2,5-Dimethylbenzaldehyde (500 mg, 3.7 mmol) and ethylenediamine (112 mg, 1.90
N N

73

mmol) were added into a 25 cm3 round bottomed flask. The procedure for [2.7] was followed and N,N-bis-(2,5-dimethylbenzylidine)-ethane-1,2-diamine was obtained as a white powder (489 mg, 88 %). M.p. 109-110 1H NMR (CDCl3) 8.58 (2H, s, C; CH=N), 7.66 (2H, s, Ar-H), 7.11 (2H, d, J = 7.1, Ar-H), 7.07 (2H, d, J = 7.8, Ar-H), 3.94 (4H, s, 2 x CH2), 2.39 (6H, s, 2 x CH3), 2.29 (6H, s, 2 x CH3);
13

C NMR (CDCl3)

161.21, 135.49, 134.92, 134.51, 131.09, 128.28, 62.15, 20.38, 18.46; IR (KBr) 3019, 2977, 2909, 2878, 2843, 1639, 1609, 1572, 1496, 1463, 1403, 1387, 1372, 1277, 1246, 1211, 1198, 1164, 1117, 1034, 1017, 969, 959, 942, 897, 822, 790, 724, 645, 505, 566, 467, 407; m/z (EI) 293 (20%), 292 ([M+], 47%), 291 (38%), 162 (42%), 161 (100%), 160 (48%), 159 (22%), 158 (39%), 147 (36%), 146 (98%), 145 (24%), 144 (49%), 134 (27%), 133 (85%), 132 (99%), 131 (59%), 130 (51%), 120 (17%), 119 (72%), 118 (26%), 117 (48%), 116 (30%), 115 (33%), 106 (26%), 105 (32%), 104 (23%), 103 (35%), 91 (52%), 79 (22%), 78 (21%), 77 (44%), 65 (19%), 51 (15%), 41 (18%), 39 (17%), 28 (17%). Anal. Calc. for C20H24N2: MW, 292.41796. Found: MW, 292.193616.
2.6.1.9 N,N-Bis-(2,4,6-trimethylbenzylidene)-ethane-1,2-diimine [2.9]

2,4,6-Trimethylbenzaldehyde (500 mg, 3.4 mmol) and ethylenediamine (101 mg, 1.70 mmol) were added into a 25 cm3 roundbottomed flask. The same procedure for
[2.7] was used and N,N-bis-(2,4,6-trimethylbenzylidine)-ethane-1,2-diamine
N N

was

obtained as a white crystalline needles (457 mg, 84 %). M.p. 126-127 1H NMR C; (CDCl3) 8.64 (2H, s, CH=N), 6.93 (4H, s, Ar-H), 4.02 (4H, s, 2 x CH2), 2.37 (12H, s, 4 x CH3), 2.28 (6H, s, 2 x CH3);
13

C NMR (CDCl3) 162.64, 139.03, 137.89, 131.41,

129.69, 63.89, 21.52, 21.06; IR (KBr) 2957, 2941, 2917, 2881, 2843, 2734, 1637, 1610, 1568, 1481, 1463, 1430, 1392, 1376, 1285, 1223, 1154, 1048, 1032, 1008, 975, 932, 897, 861, 841, 789, 727, 597, 565, 542, 512, 440; m/z (EI) 321 (8%), 320 ([M+], 21%), 176 (34%), 174 (94%), 173 (32%), 172 (32%), 161 (27%), 160 (83%), 159 (15%), 158 (32%), 148 (18%), 147 (67%), 146 (100%), 145 (49%), 144 (37%), 133 (39%), 132 (26%), 131 (31%), 130 (32%), 120 (18%), 119 (12%), 117 (18%), 116 (14%), 115 (21%), 105 (27%), 91 (26%), 77 (14%), 41 (15%). Anal. Calc. for C22H28N2: MW, 320.47112. Found: MW, 320.1650. 74

2.6.2 Reduction of bisferrocenylimines and arybisimines 2.6.2.1 N,N-Ethylenebis(ferrocenylmethyl)amine [2.10]

To a solution of lithium aluminium hydride (17 mg, 0.44 mmol) in diethyl ether (40 cm3) was added N,N-ethylenebis(ferrocenylmethylidene)imine
Fe C H2

H N

(CH2)

H N C H2 Fe

(100 mg, 0.22 mmol). The resultant mixture was heated under reflux for 1 h, and the reaction was quenched with ethyl acetate/ice-water slurry. The solution was extracted with diethyl ether (2 x 30 cm3) and the combined ethereal extracts were dried over anhydrous sodium sulfate. The solution was filtered and the solvent removed in vacuo. N,N-Ethylenebis(ferrocenylmethyl)amine was obtained as a light yellow powder (88 mg, 87 %). M.p. 82-84 1H NMR (CDCl3) 4.23 (4H, t, J = 1.8, C; C5H4), 4.18 (4H, t, J = 1.9, C5H4), 4.15 (10H, s, C5H5), 3.58 (4H, s, 2 x CH2), 2.84 (4H, s, 2 x CH2), 2.27 (2H, br-s, 2 x NH);
13

C NMR (CDCl3) 86.79, 69.18, 68.97,

68.62, 48.72, 30.06; IR (KBr) 3098, 2957, 2925, 2854, 1665, 1626, 1590, 1558, 1472, 1430, 1406, 1364, 1314, 1286, 1263, 1245, 1122, 1105, 1084, 1037, 1025, 1001, 819, 771, 668, 649, 637, 497, 482, 452; m/z (EI) 457 ([M+ +1], 8%), 456 ([M+], 6%), 455 (2%), 289 (9%), 257 (4%), 199 (100%), 154 (48%), 136 (49%); Anal. Calc. for C24H28N2Fe2: MW, 456.18252. Found: MW, 456.19.
2.6.2.2 N,N-Propylenebis(ferrocenylmethyl)amine [2.11]

To a solution of lithium aluminium hydride (21 mg, 0.56 mmol) in diethyl ether (40 cm3) was added N,N-propylenebis(ferrocenylmethylidene)imine (131 mg, 0.28 mmol). The procedure for [2.10] was
Fe C H2

H N (CH2)

H N C H2 Fe

followed and N,N-propylenebis(ferrocenylmethyl)amine was obtained as a yellow powder (121 mg, 92 %). M.p. 86-88 1H NMR (CDCl3) 4.18 (4H, t, J = 1.6, C5H4), C; 4.16 (10H, s, C5H5), 4.13 (4H, t, J = 1.6, C5H4), 3.53 (4H, s, 2 x CH2), 2.72 (4H, t, J = 6.8, 2 x CH2), 2.02 (2H, br-s, 2 x NH), 1.72 (2H, m, CH2);
13

C NMR (CDCl3) 86.78,

68.90, 68.83, 68.25, 49.36, 48.45, 30.08; IR (KBr) 3102, 2928, 2831, 1556, 1468,

75

1435, 1411, 1402, 1390, 1262, 1103, 1062, 1035, 1018, 1001, 929, 825, 807, 776, 668, 646, 499, 490, 470; m/z 471 ([M+ +1], 16%), 470 ([M+], 8%), 307 (8%), 289 (8%), 199 (100%). Anal. Calc. for C25H30N2Fe2: MW, 470.2091. Found: MW, 469.9878.
2.6.2.3 N,N-Butylenebis(ferrocenylmethyl)amine [2.12]

To a solution of lithium aluminium hydride (32 mg, 0.83 mmol) in diethyl ether (40 cm3) was added N,Nbutylenebis(ferrocenylmethylidene)imine 0.42 mmol). The procedure for (200 mg, was
[2.10]
Fe C H2

H N (CH2)

H N C H2 Fe

followed

and

N,N-

butylenebis(ferrocenylmethyl)amine was obtained as a yellow powder (174 mg, 86 %). M.p.98-99 1H NMR (CDCl3) 4.19 (4H, t, J = 1.8, C5H4), 4.13 (10H, s, C5H5), C; 4.12 (4H, t, J = 1.9, C5H4), 3.54 (4H, s, 2 x CH2), 2.65 (4H, t, J = 6.4, 2 x CH2), 2.07 (2H, br-s, 2 x NH), 1.25 (4H, m, 2 x CH2);
13

C NMR (CDCl3) 86.59, 68.97, 68.84,

68.31, 49.56, 49.22, 28.26; IR (KBr) 3098, 3056, 2896, 2866, 2801, 1471, 1453, 1442, 1410, 1396, 1383, 1318, 1259, 1227, 1151, 1114, 1105, 1045, 1037, 1028, 998, 968, 923, 900, 878, 857, 848, 834, 804, 774, 737, 724, 623, 517, 498, 487, 463, 415; m/z 485 ([M+ +1], 21%), 484 ([M+], 9%), 483 (4%), 307 (5%), 285 (6%), 199 (100%). Anal. Calc. for C26H32N2Fe2: MW, 484.23568. Found: MW, 484.09989.
2.6.2.4 N,N-Hexylenebis(ferrocenylmethyl)amine [2.13]

To a solution of lithium aluminium hydride (30 mg, 0.78 mmol) in diethyl ether (40 cm ) was added N,Nhexylenebis(ferrocenylmethylidene)imine (200 mg, 0.39 mmol). The procedure for [2.10] was followed
Fe
3

H N (CH2) C H2

H N C H2 Fe

and N,N-hexylenebis(ferrocenylmethyl)amine was obtained as a yellow powder (183 mg, 91 %). M.p. 102-103 1H NMR (CDCl3) 4.20 (4H, t, J = 1.8, C5H4), 4.13 (10H, C; s, C5H5), 4.12 (4H, t, J = 1.8, C5H4), 3.52 (4H, s, 2 x CH2), 2.63 (4H, t, J = 7.1, 2 x CH2), 1.53 (2H, br-s, 2 x NH), 1.35 (4H, m, 2 x CH2), 1.77 (4H, m, 2 x CH2);
13

(CDCl3) 87.16, 68.90, 68.83, 68.25, 49.90, 49.44, 30.34, 27.69; IR (KBr) 3098, 2924, 2849, 2818, ,1478, 1452, 1434, 1309, 1247, 1227, 1210, 1153, 1121, 1105, 1043, 1021, 1000, 960, 923, 873, 822, 768, 731, 692, 665, 615, 520, 489, 481; m/z 513 76

([M+ +1], 9%), 512 (10%), 511 (4%), 313 (7%), 307 (3%), 289 (3%), 199 (100%), 154 (22%). Anal. Calc. for C28H36N2Fe2: MW, 512.28884. Found: MW, 511.7.
2.6.2.5 N,N-Octylenebis(ferrocenylmethyl)amine [2.14]

To a solution of lithium aluminium hydride (19. mg, 0.52 mmol) in diethyl ether (40 cm3) was added N,N-octylenebis(ferrocenylmethylidene)imine (137 mg, 0.26 mmol). The procedure for [2.10] was
Fe C H2

H N (CH2)

H N C H2 Fe

followed and N,N-octylenebis(ferrocenylmethyl)amine was obtained as a yellow powder (121 mg, 88 %). M.p. 65-66 1H NMR (CDCl3) 4.20 (4H, t, J = 1.7, C5H4), C; 4.13 (10H, s, C5H5), 4.13 (4H, C5H4), 3.52 (4H, s, 2 x CH2), 2.62 (4H, t, J = 7.0, 2 x CH2), 1.67 (2H, br-s, 2 x NH), 1.49 (4H, m, 2 x CH2), 1.31 (8H, s, 4 x CH2);
13

C NMR

(CDCl3) 87.28, 68.88, 68.79, 68.15, 50.03, 49.46, 30.39, 29.88, 27.71; IR (KBr) 3095, 2923, 2852, 1473, 1432, 1409, 1326, 1240, 1150, 1120, 1105, 1044, 1018, 999, 961, 923, 884, 864, 848, 819, 772, 723, 668, 614, 523, 501, 484, 456; m/z 541 ([M+ +1], 15%), 540 ([M+], 23%), 342 (5%), 341 (15%), 215 (4%), 199 (100%). Anal. Calc. for C30H40N2Fe2: MW, 540.342. Found: MW, 539.9.
2.6.2.6 N,N-Bis(2,3-dimethylbenzyl) ethane-1,2-diamine[2.15]

To a solution of lithium aluminium hydride (17 mg, 0.44 mmol) in diethyl ether (40 cm3) was added N,N-bis(2,3-dimethylbenzylidene)ethane-1,2diimine (65 mg, 0.22 mmol). The procedure for [2.10] was followed and N,N-bis(2,3-dimethylbenzyl)ethane-1,2-diamine
1

N H

H N

was

obtained as a colourless oil (37 mg, 56%). M.p.; H NMR (CDCl3) 7.18-7.15 (2H, m, Ar-H), 7.11 (4H, br-s, Ar-H), 3.81 (4H, s, 2 x CH2), 2.86 (4H, s, 2 x CH2), 2.32 (6H, s, 2 x CH3), 2.28 (6H, s, 2 x CH3), 1.78 (2H, s, 2 x NH); 13C NMR (CDCl3) 138.4, 137.7, 137.5, 135.4, 129.2, 127.1, 125.8, 52.7, 49.5, 21.0, 15.2; IR (NaCl) 3308, 3066, 3030, 3013, 2937, 2915, 2821, 2732, 2691, 1588, 1463, 1383, 1353, 1330, 1295, 1248, 1183, 1163, 1115, 1090, 1018, 990, 972, 902, 880, 820, 774, 725, 710, 675, 666; m/z; 297 ([M+ +1], 90%), 296 ([M+], 8%), 295 (25%), 171 (5%), 148 (28%), 119 (100%). Anal. Calc. for C20H28N2: MW, 296.44972. Found: MW, 296.1094. 77

2.6.2.7 N,N-Bis(2,5-dimethylbenzyl) ethane-1,2-diamine [2.16]

N,N-Bis(2,5-dimethylbenzylidene)ethane-1,2diimine (131 mg, 0.44 mmol) was added to a solution of lithium aluminium hydride (34 mg, 0.88 mmol) in diethyl ether (40 cm3). The procedure for [2.10] was followed and N,Nbis(2,5-dimethylbenzyl)ethane-1,2-diamine was obtained as a white powder (87 mg, 68%). M.p. 43-46 1H NMR (CDCl3) 7.13 (2H, s, Ar-H), 7.06 (2H, d, J = 7.6, Ar-H), C; 6.99 (2H, d, J = 7.6, Ar-H), 3.76 (4H, s, 2 x CH2), 2.86 (4H, s, 2 x CH2), 2.32 (6H, s, 2 x CH3), 2.31 (6H, s, 2 x CH3), 2.00 (2H, s, 2 x NH); 13C NMR (CDCl3) 138.12, 135.77, 133.42, 130.60, 129.64, 128.07, 51.77, 49.24, 21.38, 18.94; IR (KBr) 3265, 3048, 3017, 2971, 2946, 2918, 2894, 2859, 2823, 2758, 2732, 2703, 1610, 1499, 1474, 1457, 1376, 1368, 1303, 1279, 1240, 1229, 1204, 1188, 1156, 1131, 1098, 1051, 1038, 995, 980, 928, 882, 833, 814, 800, 718, 704, 668, 544, 492, 440, 419 ; m/z 297 ([M+ +1], 51%), 296 ([M+], 6%), 295 (18%), 167 (9%), 148 (22%), 119 (100%). Anal. Calc. for C20H28N2: MW, 296.44972. Found: MW, 296.2178
2.6.2.8 N,N-Bis(2,4,6-trimethylbenzyl) ethane-1,2-diamine[2.17]
N H H N

N,N-Bis(2,4,6-trimethylbenzylidene) ethane1,2-diimine (100 mg, 0.31 mmol) was added to a solution of lithium aluminium hydride (25 mg, 0.66 mmol) in diethyl ether (40 cm3). The procedure for [2.10] was followed and N,N-bis(2,4,6-trimethylbenzyl) ethane-1,2-diamine was obtained as a white powder (79 mg, 79 %). M.p.: 69-72 C;
1

N H

H N

H NMR (CDCl3) 6.85 (4H, s, Ar-H), 3.81 (4H, s, 2 x CH2)), 2.92 (4H, s, 2 x CH2),
13

2.33 (12H, s, 4 x CH3), 2.26 (6H, s, 2 x CH3), 1.99 (2H, s, 2 x NH);

C NMR (CDCl3)

137.6, 137.4, 129.6, 129.5, 48.2, 47.2, 21.3, 20.1; IR (KBr) 3202, 3005, 2957, 2926, 2845, 2817, 2789, 1613, 1483, 1461, 1443, 1378, 1355, 1345, 1332, 1262, 1222, 1209, 1129, 1110, 1091, 1029, 1014, 914, 867, 851, 825, 807, 774, 759, 709, 665, 619, 592, 549; m/z 325 ([M+ +1], 37%), 324 ([M+], 4%), 323 (7%), 307 (8%), 297

78

((14%), 154 (19%), 133 (100%), 120 (44%). Anal. Calc. for C22H32N2: MW, 324.50288. Found: MW, 324.2869.

2.7 References
1. C. Imrie, V. O. Nyamori and T. I. A. Gerber, J. Organomet. Chem., 689 (2004) 1617-1622. 2. A. Benito, J. Cano, R. Martnez-Mez, J. Soto, J. Pay, F. Lioret, M. Julve, J. Faus and M. Dolores Marcos, Inorg. Chem., 32 (1993) 1197-1203. 3. V. K. Muppidi, T. Htwe, P. S. Zcharias and S. Pal, Inorg. Chem. Commun., 7 (2004) 1045-1048. 4. I. Ratera, D. Ruiz-Molina, C. Snchez, R. Alcal, C. Rovira and J. Veciana, Synth. Met., 121 (2001) 1834. 5. J. Rajput, PhD Thesis: Platinum group metal coordination complexes of ferrocenyl-N-donor ligands and their potential application in catalysis and medicinal chemistry, University of Cape Town, 2003, 34. 6. H. Naeimi, F. Salimi and K. Rabiei, J. Mol. Cat. A, 260 (2006) 100-104. 7. M. Woltersdorf, R. Kranich and H.-G. Schmalz, Tetrahedron, 53 (1997) 7219. 8. R. M. Silverstein, F. X. Webster and D. J. Kiemle, Spectroscopic Identification of Organic Compounds, 7th Ed., John Wiley & Sons, Inc. 2005. 9. R. C. J. Atkinson, V. C. Gibson and N. J. Long, Chem. Soc. Rev., 33 (2004) 313. 10. B. S. Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell, Vogels Textbook of Practical Organic Chemistry, Longman Scientific and Technical, England (5th Ed), 1989.

79

CHAPTER 3
RESULTS AND DISCUSSION

3.1 Synthesis of cationic rhodium(I) complexes

3.1.1 Rhodium(I) complexes containing bisferrocenylimines

The bisferrocenylimines described in the previous chapter were prepared in order for them to be reacted with a rhodium(I) metal centre, to form cationic rhodium(I) complexes. Rhodium(I) is understood to form square planar coordination complexes with -acceptor ligands and some five-coordinate complexes are known as well.1 Cationic rhodium complexes are known for their application in the field of catalysis. An appropriate metal precursor for the synthesis of rhodium(I) complexes is the chloro-bridged rhodium cyclooctadienyl dimer, chloro(1,5-cyclooctadiene)rhodium(I). The dimer can readily be obtained from the reaction of 1,5-cyclooctadiene with rhodium trichloride trihydrate under reflux.1 The type of complex formed from the dimer is dependent on the nature of the ligand and the ratio of the metal to ligand.2 The cationic rhodium(I) complexes were synthesized using a literature procedure as illustrated in Scheme 3.1.3 A solution of silver perchlorate in acetone was added to a solution of the rhodium dimer in acetone. On precipitation of silver chloride, a solvated complex of general formula [Rh(COD)(acetone)2]ClO4 was formed.3,4 The addition of a bisferrocenylimine ligand resulted in a cationic complex by displacement of the coordinated solvent from the rhodium coordination sphere. The complexes [3.1] (x = 2), [3.2] (x = 3) and [3.3] (x = 4) were obtained in low to excellent yields by redissolving the residue, after concentration of solvent, with dichloromethane and precipitated by addition of diethyl ether. The complexes were further purified by recrystallization. Complex [3.2] had the highest yield while [3.1] was obtained in lowest yield. This effect was attributed to the stability of the sixmembered ring formed by the bidentate ligand [2.2] with the metal centre compared to five- and seven-membered rings formed by [2.1] and [2.3], respectively. Attempts to prepare complexes containing [2.4], [2.5] and [2.7]-[2.9] were not successful. 80

Cl Rh Cl [3.0] Rh
+ 2 AgClO4

acetone

[Rh(COD)(acetone)2]ClO4 +

AgCl(s)

2L

x = 2: [3.1] = 3: [3.2] = 4: [3.3]

N CH Fe

(CH2) Rh

N CH Fe ClO4

Scheme 3.1: Procedure for the synthesis of cationic rhodium(I) complexes.3

1

H NMR data for [3.1]-[3.3] is summarized in Table 3.1. The imine (CH=N) chemical

shifts for [3.2] and [3.3] were observed in the expected region while for [3.1] the peak was shifted remarkably to lower frequencies. This effect has also been observed by Lee et al.3 and could not be explained (Figure 3.1). The CH=N signal in
[3.1] moved from 8.17 ppm in the free ligand to 7.42 ppm in the complex. The

CH=N signal moved to higher frequencies for [3.2] and [3.3]. This signal was observed to have shifted from 8.17 ppm in the free ligand [2.2] to 8.31 ppm in the complex. On the other hand, the signal for [3.3] moved from 8.18 ppm in the free ligand [2.3] to 8.22 ppm in the complex. In the ferrocene region, a sharp singlet was observed at 4.37 and 4.07 ppm for [3.1] and [3.2] respectively, and it was assigned to the unsubstituted Cp ring. Two singlets at 4.73 and 4.80 ppm for [3.1] were assigned to the substituted Cp ring. The substituted Cp ring signals for [3.2] were observed at 4.23 and 4.72 ppm. The appearance of additional signals in the ferrocene region of [3.3] complicated the assignments.

81

Table 3.1: The summarized NMR data for [3.1]-[3.3] Complex Yield (%)a
1

H (ppm)

13

C (ppm)

CH=N 7.42

COD 4.16, 2.64, 2.09,

Fc 4.80, 4.73, 4.37 4.72, 4.23, 4.07

c

CH=N 168.48

COD 30.55

Fc 73.22, 70.68, 84.65

84.49, 74.70,

[3.1]

32 (47.0)
b

8.31
[3.2]

5.48, 5.39, 2.58, 1.97

170.44

75.61, 71.73, 30.89 70.51, 70.28, 84.89

84 (37.1)b 8.22

6.11, 5.65, 2.62, 1.79

170.39

75.63, 31.26

[3.3]

70 (39.0)b

a b
c

Isolated yields are based on starting reagents. Numbers in parentheses are conductivity values in Ohm-1.cm2.mol-1 The appearance of additional signals in the ferrocene region complicated the assignments.

Two sharp and equally intense singlets were observed at 4.26 and 4.14 ppm and are assigned to the unsubstituted Cp rings. This suggests that the Cp rings could be chemically inequivalent due to the spatial orientation of the ferrocene, something that was not observed in [3.1] and [3.2]. Other signals could not be assigned due to the complexity of the signals in the region. Initially, it was thought that the extra signals were due to the presence of impurities. However, the signals were persistent even after recrystallization several times. The COD ligand exhibited the expected patterns for [3.1] giving rise to a singlet due to CH=CH protons at 4.16 ppm, a multiplet 2.64 ppm and a doublet 2.09 ppm due to CH2 protons. For [3.2] and [3.3] the CH=CH proton signal was split into two singlets at 5.48 and 5.39 ppm and 6.11

82

and

5.65

ppm,

respectively.

The

CH2

signals

were

Figure 3.1: 1H NMR spectra of [3.2] (top) and [3.3] (bottom) in CDCl3

observed in the expected region for both [3.2] and [3.3].

13

C NMR showed the

exhibited C=N signals in the expected region, 168.48, 170.44 and 170.39 ppm for
[3.1], [3.2] and [3.3], respectively. The ferrocene signals for [3.1] and [3.2] were

observed in the expected region while the same problem as with the 1H NMR was experienced for [3.3]. The COD signals were also observed in the expected region 83

for all complexes. IR spectra of all the compounds showed that the v(C=N) stretching signals have moved to lower frequencies. The infrared together with the NMR information explain the coordination of the ligands to the rhodium metal centre.

3.1.2 X-ray Crystallography

Crystals of [3.2] that were suitable for X-ray crystallographic analysis were obtained by slow diffusion of diethyl ether into a solution of the complex in dichloromethane. The complex was observed to crystallize in a triclinic space group P1bar with Z = 4 and contains two molecules (structural isomers) in an asymmetric unit. The structure was refined successfully with the final R factor of 0.0456.
Table 3.2: Crystal data and structure refinement of [3.2] and [3.3] Complex [3.2]
Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions a b c Volume Z Calculated density Reflections collected Unique Goodness-of-fit on F Final R indices R indices (all data)
2

Complex [3.3]
C34H40ClFe2N2O4Rh 790.74 173(2) K 0.71073 Monoclinic P21/c 12.983(3) 13.536(2) 17.729(4) 90 92.580(7) 90

C33H38ClFe2N2O4Rh 776.71 113(2) K 0.71073 Triclinic P1bar 12.0890(2) 16.5931(2) 17.5512(3) 67.8240(10) 72.9460(10) 72.3860(10) 3042.77(8) A 4 1.696 Mg/m
3 3

3112.6(11) A3 4 1.687 Mg/m3 48758 / 5716 [R (int) = 0.1694 1.034 R1 = 0.0611, wR2 =0.0934 R1 = 0.1324, wR2 = 0.1119

70435 / 11534 [R (int) = 0.1029 1.023 R1 = 0.0456, wR2 = 0.0875 R1 = 0.0758, wR2 = 0.0987

84

All hydrogen atoms were placed geometrically with fixed bond length and refined with isotropic displacement parameters depending on their carbon atoms. The parameters for crystal data collection and structure refinements are in Table 3.2. The ORTEP drawing shown in Figure 3.2 confirms the molecular structure of [3.2]. The bond lengths, angles, torsion angles and other parameters are in Table 3.3. The rhodium atom is oriented in an essentially square planar geometry defined by two nitrogen atoms of the bidentate ligand and the two C=C double bonds of the COD ligand.

Figure 3.2: ORTEP diagram of [3.2]

The six-membered ring formed by the rhodium atom, the two nitrogen atoms of the ligand and the three carbon atoms of the alkyl chain separating the two nitrogen atoms is in a chair conformation. The chair conformation is the lowest energy state that a six-membered ring can be found in, which explains the reason for [3.2] being obtained in excellent yields. The Rh(1A)-N(1A) and Rh(1A)-N(2A) bond distances for molecule A are 2.077(4) and 2.095(4) , respectively. For molecule B, the Rh(1B)85

N(2B) and Rh(1B)-N(1B) the bond distances are 2.076(4) and 2.088(4) , respectively. The bond distances Rh(1A)-C(2A), Rh(1A)-C(6A), Rh(1A)-C(1A) and Rh(1A)-C(5A) for molecule A, are 2.144(4), 2.150(5), 2.152(4) and 2.158(4) , respectively. On the other hand, for molecule B the bond distances Rh(1B)-C(2B), Rh(1B)-C(5B), Rh(1B)-C(6B) and Rh(1B)-C(1B) are 2.130(4), 2.143(4), 2.144(4) and 2.171(4) , respectively.
Table 3.3: Selected bond distances, bond angles and torsion angles of [3.2] Molecule A
Rh(1A)-N(1A) Rh(1A)-N(2A) Rh(1A)-C(2A) Rh(1A)-C(6A) Rh(1A)-C(5A) Rh(1A)-C(2B) N(1A)-C(9A) N(2A)-C(13A) N(1A)-(Rh(1A)-N(2A) N(1A)-(Rh(1A)-C(2A) N(2A)-(Rh(1A)-C(2A) N(1A)-(Rh(1A)-C(6A) N(2A)-(Rh(1A)-N(6A) C(2A)-(Rh(1A)-N(CA) N(2A)-Rh(1A)-N(2A)-C(9A) C(2A)-Rh(1A)-N(1A)-C(9A) C(6A)-Rh(1A)-N(1A)-C(9A) C(1A)-Rh(1A)-N(1A)-C(9A) C(5A)-Rh(1A)-N(1A)-C(9A) N(2A)-Rh(1A)-N(1A)-C(10A) 2.077(4) 2.095(4) 2.144(4) 2.150(5) 2.152(4) 2.158(4) 1.294(6) 1.277(5) 85.92(14) 92.34(16) 171.25(16) 154.73(17) 89.01(16) 96.11(18) 112.4(4) -59.0(4) -168.7(4) -96.7(4) 3.1(10) -65.1(3)

Molecule B
Rh(1B)-N(2B) Rh(1B)-N(1B) Rh(1B)-C(2B) Rh(1B)-C(5B) Rh(1B)-C(6B) Rh(1B)-C(1B) N(1B)-C(9B) N(2B)-C(13B) N(2B)-(Rh(1B)-N(1B) N(2B)-(Rh(1B)-C(2B) N(1B)-(Rh(1B)-C(2B) N(2B)-(Rh(1B)-C(5A) N(1B)-(Rh(1B)-C(5A) C(2B)-(Rh(1B)-C(5A) N(2B)-Rh(1B)-N(1B)-C(9B) C(2B)-Rh(1B)-N(1B)-C(9B) C(5B)-Rh(1B)-N(1B)-C(9B) C(6B)-Rh(1B)-N(1B)-C(9B) C(1B)-Rh(1B)-N(1B)-C(9B) N(2B)-Rh(1B)-N(1B)-C(10B) 2.076(4) 2.088(4) 2.130(4) 2.143(4) 2.144(4) 2.171(4) 1.289(6) 1.286(6) 85.06(14) 162.39(16) 95.29(16) 95.04(16) 174.44(16) 82.94(18) 112.8(4) -49.6(4) 21.5(19) -163.7(4) -86.9(4) -65.5(3)

The bond distances that have just been mentioned were found to be comparable to with literature-cited bond distances for similar complexes.5 The bite angles N(1A)Rh(1A)-N(2A) and N(2B)-Rh(1B)-N(1B) are 85.92(14) and 85.06(14) for molecule A and molecule B, respectively. The deviation from the ideal 90 bond angles (square planar) around the Rh-atom was due to the steric bulk of the COD ligand.5 The bond distances N(1A)-C(9A) and N(2A)-C(13A) are 1.294(6) and 1.277(5) and are typical

86

bond distances for the C=N bond. The crystal packing in the unit cell of [3.2] is shown in Figure 3.3 and no intermolecular interactions were exhibited.

Figure 3.3: Crystal packing of [3.2], projection viewed along [100]

Crystals of [3.3] that were suitable for X-ray crystallographic analysis were obtained by slow diffusion of diethyl ether into a solution of the complex in dichloromethane. The complex was observed to crystallize in a monoclinic space group P21/c with Z = 4. The structure was refined successfully with the final R factor of 0.0611. All hydrogen atoms were fixed in geometrically calculated positions with Uiso set at 1.2 or 1.5 those of the parent atoms. The parameters for crystal data collection and structure refinements are in Table 3.2. The ORTEP drawing shown in Figure 3.4 confirms the molecular structure of [3.3]. The bond lengths, angles, torsion angles and other parameters are in Table 3.4. The rhodium atom is oriented in an essentially square planar geometry defined by two nitrogen atoms of the bidentate ligand and the two C=C double bonds of the COD ligand.

87

Figure 3.4: ORTEP drawing of [3.3]

Figure 3.5: Crystal packing of [3.3], projection viewed along [100]

The Rh(1)-N(1) and Rh(1)-N(2) bond distances are 2.089(5) and 2.105(5) and are slightly longer than those for [3.2]. The Rh(1)-C(6), Rh(1)-C(2), Rh(1)-C(5) and Rh(1)-C(1) are 2.135(6), 2.146(6), 2.150(60) and 2.165(6) , respectively. The bite angle N(1)-Rh(1)-N(2) is 89.04(18) and is much closer to the ideal 90 for square planar complex. Figure 3.5 shows the crystal packing in the unit cell of [3.3] and no

88

intermolecular interactions are present. The crystal packing of [3.2] completely differs from that of [3.3].
Table 3.4: Selected bond distances, bond angles and torsion angles of [3.3] Bond distances
Rh(1)-N(1) Rh(1)-N(1) Rh(1)-C(6) Rh(1)-C(2) Rh(1)-C(5) Rh(1)-C(1) N(1)-C(9) N(1)-C(10) N(2)-C(14) N(2)-C(13) C(9)-C(21) C(10)-C(11) C(11)-C(12) C(12)-C(13) C(14)-C(41) 2.089(5) 2.105(5) 2.135(6) 2.146(6) 2.150(6) 2.165(6) 1.283(7) 1.478(7) 1.289(7) 1.473(7) 1.450(8) 1.512(8) 1.522(8) 1.522(8) 1.470(8)

Bond angles
N(1)-Rh(1)-N(2) N(1)-Rh(1)-C(6) N(2)-Rh(1)-C(6) N(1)-Rh(1)-C(2) N(2)-Rh(1)-C(2) C(6)-Rh(1)-C(2) N(1)-Rh(1)-C(5) N(2)-Rh(1)-C(5) C(6)-Rh(1)-C(5) C(2)-Rh(1)-C(5) 89.04(18) 158.7(2) 92.9(2) 89.7(2) 153.2(2) 97.8(2) 163.6(2) 91.8(2) 37.6(2) 82.2(2)

Torsion angles
N(2)-Rh(1)-N(1)-C(9) C(6)-Rh(1)-N(1)-C(9) C(2)-Rh(1)-N(1)-C(9) C(1)-Rh(1)-N(1)-C(9) 107.9(5) 12.3(9) -98.8(5) -61.4(5)

N(2)-Rh(1)-N(1)-C(10) -76.6(4) C(2)-Rh(1)-N(1)-C(10) .76.7(4) C(1)-Rh(1)-N(2)-C(14) 7.4(14)

C(10)-(11)-C(12) 116.1(5) C(13)-C(12)-C(11) 114.7(5) C(25)-C(21)-C(22) 106.6(6) C(25)-C(21)-C(9) 130.7(6) C(22)-C(21)-C(9) 122.4(6)

3.1.3 Rhodium(I) complexes containing bisferrocenylamines

Initially, the objective was to synthesize rhodium complexes similar to those reported by Kim and Alper (Figure 3.6)6 using bisferrocenylamines as ligands. These complexes are said to be highly effective in hydroformylation reactions.
-

+
N Rh N Cl Rh

Cl

Figure 3.6: Cationic rhodium(I) diamine complexes with the [Rh(COD)Cl2]- anion.6

89

The complexes were prepared by stirring equimolar amounts (1 mole) of [Rh(COD)Cl]2 [3.0] with bisferrocenylamines [2.10]-[2.12], using the Schlenk technique, at room temperature in an argon environment, for 12 h.6 Yellow precipitates were formed, almost immediately, on addition of the ligand to a solution of [Rh(COD)Cl]2 in toluene. However, these complexes were highly insoluble in most organic solvents and therefore could not be characterized. The insolubility of the complexes was thought to be due to very high lattice energies in the molecules. It was then decided that a smaller counterion should be used instead of the bulky anionic complex. Tetrafluoroborate ion, BF4- was chosen as the anion to be used and all the complexes were soluble in most organic solvents, making characterization possible. The complexes were prepared by a slightly modified literature method.4 Silver tetrafluoroborate (AgBF4) (2 mol) in acetone was added to [Rh(COD)Cl]2 (1 mol) in acetone using the Schlenk technique in an argon atmosphere. After filtration of the precipitated AgCl, the yellow filtrate was treated with the appropriate ligand (2 mol) in acetone. The mixture was stirred at room temperature for 24 h. Addition of n-pentane caused the precipitation of a yellow solid after the volume of acetone was reduced to approximately 5 cm3. The complexes (Figure 3.7) were further purified by recrystallization and were isolated in moderate to excellent yields (Table 3.5).

H N Fe C H2

(CH2) Rh

H N C H2 Fe

BF4

X = 2 [3.4] = 3 [3.5] = 4 [3.6]

Figure 3.7: Cationic rhodium(I) complexes

90

Surprisingly, 1H NMR data was not helpful in terms of the characterization of all complexes since their spectra showed only broad signals. 13 C NMR gave no signals for complexes even after running the experiment for 24 h. IR spectra of complexes
[3.4], [3.5] and [3.6] showed absorptions in the region 3180-3280 cm-1 representing

the v(NH) stretching frequencies. The frequencies were similar to those reported by Garrald et al2 and Beller et al.7 for (NH) of similar complexes. For ferrocene, three bands were observed in all complexes in the regions 3090-3100 cm-1, 1405-1415 cm-1 and 1104-1115 cm-1, which were assigned to v(CH) stretching, v(C-C) stretching and ring breathing, respectively.1

Figure 3.8: IR spectrum of [3.5]

Complexes [3.4], [3.5] and [3.6] each exhibited a band at 1642, 1634 and 1638, respectively, which was attributed to the v(C=C) stretching frequency of the COD ligand. Another sharp band was observed in the region 480-490 cm-1 and it was assigned to the Rh-N stretching frequency. A signal at around 1000 cm-1 was observed in all complexes which, according to Beller et al.,8 could be assigned to the BF4- ion, indicative of a cationic species. The infrared spectrum of [3.5] is shown in Figure 3.8.

91

Table 3.5: Table of yields and conductivity measurements Number Complex Yield (%)

m
(Ohm-1.cm2.mol-1)

H N

(CH 2) Rh

[3.4]

Fe

C H2

H N C H2 Fe

BF 4

66

37.6

H N

(CH 2) Rh

[3.5]

Fe

C H2

H N C H2 Fe

BF 4

82

40.4

H N

(CH 2) Rh

[3.6]

Fe

C H2

H N C H2 Fe

BF 4

72

33.6

H N

(CH 2 ) Rh

[3.7]

C H2

H N C H2 BF 4

60

32.0

H N

(CH 2) Rh

[3.8]

C H2

H N C H2 BF 4

68

42.8

The aromatic v(C=C) stretching frequencies were observed at 1506 cm-1 for [3.7] and 1509 cm-1 for [3.8]. A Rh-N stretching band was also observed for [3.7] and
[3.8] in exactly the same region as in the previous complexes.

A sharp band that was assigned to the BF4- ion was observed at 1032 and 1036 cm-1 for both complexes. This was an indication of the cationic nature of the complexes. The conductivity values of the complexes (Table 3.5) were comparable to the conductivity values obtained by Denise and Pannetier9 for similar types of complexes.

92

Figure 3.9: IR spectrum of [3.8]

3.2 Electronic spectroscopy

Uv-vis spectra of all complexes were obtained in a dichloromethane solution (10-4 M). In comparison with the free ligands [2.1], [2.2] and [2.3], spectra of complexes
[3.1], [3.2] and [3.3] exhibited an extra band at max 350, 382 and 383 nm,

respectively (Figure 3.12, Table 3.6). Moreover, the bands that were observed in the ligands [2.1]-[2.3] appeared to have shifted to higher wavelengths max. This was clearly indicative of some coordination to the rhodium(I) ion. Both bands at lower wavelengths, for the complexes, appeared as shoulders. UV-vis spectra of complexes [3.4], [3.5] and [3.6] exhibited a shoulder at max 462, 466 and 468 nm, respectively, (Figure 3.11, Table 3.6). Bands at max 385, 388 and 387 nm in [3.4],
[3.5] and [3.6], respectively, were thought to be due to coordination to the rhodium

metal. This band appeared in complexes [3.1]-[3.3] as well as in complexes [3.7] and [3.8] as will been seen later. One band that was observed in the corresponding ligands
[2.10], [2.11] and [2.12] was not observed in the spectra of the complexes. It was

postulated that these bands could have been masked by the bands at max 388, 387 and 382 nm. 93

Figure 3.10: UV-vis spectra of [3.1], [3.2] and [3.3]

Figure 3.11: UV-Vis spectra of [3.4], [3.5] and [3.6]

UV-vis spectra of complexes [3.7] and [3.8] exhibited only one band at max 382 and 381 nm respectively (Figure 3.10, Table 3.5). These spectra clearly showed ligand coordination to the metal since [2.16] and [2.17] were inactive in the UV-vis region (800-200 nm).

94

Figure 3.12: UV-vis spectra of [3.7] and [3.8] Table 3.6: UV-vis data for complexes [3.1]-[3.8] Complex [3.1] [3.2] [3.3] [3.4] [3.5] [3.6] [3.7] [3.8]
= molar exctinction coefficient.

max (nm) (L.mol-1.cm-1) 303 (1198) 347 (593) 348 (711) 350 (670) 382 (392) 383 (456) 385 (174) 388 (345) 387 (219) 382 (228) 381 (141) 469 (219) 469 (469) 467 (282) 462 (34) 466 (50) 468 (32)

3.3 Cyclic Voltammetry

Some typical voltammograms of selected rhodium(I) complexes are illustrated in Figure 3.13, and depict one-electron reversible redox waves.

95

Figure 3.13: Cyclic voltammograms of [3.2], [3.4], [3.5] and [3.6]

Rhodium(I) complexes containing bisferrocenylimines exhibited positive shifts in potential meaning that the complexes became more resistant to oxidation than their corresponding free ligands (Figure 2.11, Table 3.6). Similarly, rhodium(I) complexes containing bisferrocenylamines exhibited positive shifts in potentials compared to their corresponding free ligands and thus became more difficult to oxidise (Figure 3.13, Table 3.6). The positive shift in potentials exhibited by the compounds was evidence that coordination to the rhodium centre had occurred. Rhodium(I) complexes containing arylbisamines [3.7] and [3.8] were electrochemically inactive as in the case of their corresponding free ligands.
Table 3.7: Half-wave potentials of [3.1]-[3.6] Compound [3.1] [3.2] [3.3] [3.4] [3.5] [3.6] Epa (mV) Epc (mV) E1/2 (mV)

413 388 372 246 222 157

342 300 261 105 104 72

327.5 344 316.5 175.5 163 114.5

96

3.4 Experimental
3.4.1 Purification procedures

All reagents and solvents were purified using standard purification and drying methods.8 Silver tetrafluoroborate and the chloro-(1,5-cyclooctadiene)rhodium(I) dimer were obtained from Sigma Aldrich Chemical Company, Milwaukee, USA.
Table 3.7: General drying agents for solvents.

Solvent Dichloromethane Hexane Toluene

Drying Agent CaH2 Na wire Na wire

3.4.2 Instrumentation

Unless otherwise mentioned, all reactions were carried out using standard Schlenk techniques in an argon gas environment. All the other instruments employed for characterizations were the same as stated in Chapter 2. X-ray crystal intensity data were collected on a Nonius Kappa-CCD diffractometer using graphite monchromated MoK radiation at the University of Cape Town. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). The strategy for the data collections was evaluated using the Bruker Nonius Collect program.9 Data were scaled and reduced using DENZO-SMN software (Ontwinowski & Minor, 1977). An empirical absorption correction utlilized the program SADABS (Sheldrick, 1996). The structure was solved by direct methods and refined by full-matrix least-squares with the program SHELXL-97 (Sheldrick, 1997), refining on F2.10,11 Packing diagrams were produced using the program PovRay and graphic interface X-seed (Barbour, 2001).12 All the non-H atoms were refined anisotropically.

97

3.5 Synthesis of rhodium(I) complexes

3.5.1 Rhodium(I) complexes containing bisferrocenylimines

3.5.1.1 General procedure3

Silver perchlorate [3.0] (0.23 mmol) (Scheme 3.1) in acetone (2 cm3) was added to a solution of the chloro-(1,5-cyclooctadiene)rhodium dimer (0.11 mmol) in acetone (30 cm3). After removal of the precipitated AgCl, the reaction mixture was then heated under reflux for 30 minutes. The reaction mixture was treated with bisferrocenylimine (0.23 mmol) in toluene (20 cm3) and the resultant dark red solution was left to stir at room temperature (ca. 25 for 3h. Solvents were removed in vacuo and the dark C) red solid was recrystallized from a dichloromethane/hexane mixture. The products were obtained as dark red to orange solids.
3.5.1.2 Complex [3.1]3

The general procedure in 3.5.1.1 was followed using N,Nethylenebis(ferrocenylmethylidene)imine

3

N CH Fe

(CH2) Rh

N CH Fe ClO4

(104

mg, 0.23 mmol) in toluene (20 cm ). Complex [3.1] was obtained as a dark red solid (27 mg, 32 %). M.p. 215 (decomp) (lit. 192 decomp.); 1H NMR (CDCl3) 7.43 (2H, s, N=CH), 4.80 C C, (4H, t, J = 1.7, C5H4), 4.73 (4H, t, J = 1.8, C5H4), 4.37 (10H, s, C5H5), 4.16 (4H, s, COD-CH), 3.85 (4H, s, CH2), 2.64 (4H, br-s, COD-CH2), 2.09 (4H, d, J = 7.5, CODCH2);
13

C NMR (CDCl3) 168.48, 84.65, 84.49, 74.71, 73.23, 70.68, 57.01, 30.55; IR

(KBr); 3249, 2951, 2886, 2836, 1612, 1447, 1412, 1377, 1259, 1219, 1098, 1102, 954, 825, 733, 622, 479; m/z (FAB) 665 ([M++2], 3%), 663 ([M+], 29%), 553 (3%), 489 (2%), 453 (9%), 333 (3%), 308 (18%), 289 (16%), 233 (4%), 154 (100). Anal.Calc. for C32H36N2Fe2Rh: MW, 663.06324. Found: MW, 662.7.

98

3.5.1.3 Complex [3.2]

The general procedure in 3.5.1.1 was followed using N,N-propylenebis(ferrocenylmethylidene)imine (107 mg, 0.23 mmol) in toluene (20 cm ). Complex [3.2] was obtained as a reddish orange solid (72 mg, 84
3
CH Fe

(CH2) Rh

N CH Fe ClO4

%). M.p. 220 (decomp.); 1H NMR 8.31 (2H, s, N=CH), 5.49 (2H, s, COD-CH), C 5.39 (2H, s, COD-CH), 4.72 (4H, s, C5H4), 4.68 (4H, s, 2 x CH2), 4.23 (4H, s, C5H4), 4.17 (2H, m, CH2), 4.07 (10H, s, C5H5), 2.59 (4H, br-s, COD-CH2), 1.97 (4H, d, J = 7.7, COD-CH2)
13

C NMR (CDCl3) 170.44, 77.62, 75.61, 73.41, 70.51, 70.28, 65.04,

30.89, 30.55; IR (KBr) 3106, 2933, 2852, 1624, 1457, 1411, 1373, 1331, 1253, 1093, 1052, 998, 897, 829, 622; m/z (FAB) 677 ([M+], 11%), 675 (2%), 567 (2%), 467 (5%), 424 (3%), 347 (2%), 307 (18%), 289 (17%), 242 (2%), 154 (100%). Anal. Calc.2 for C33H38N2Fe2Rh; C, 51.03; H, 4.93; N, 3.61; MW, 677.26372. Found: C, 50.27; H, 4.59; N, 3.48; MW, 676.7.
3.5.1.4 Complex [3.3]

The general procedure in 3.5.1.1 was followed using N,N-butylenebis(ferrocenlmethylidene)imine (111 mg, 0.23 mmol). Complex [3.3] was obtained as an orange solid (68.3 mg, 70%). M.p. 228 C
CH Fe

(CH2) Rh

N CH Fe ClO4

(decomp.); 1H NMR (CDCl3) 8.22 (2H, s, CH=N), 6.11 (2H, s, COD-CH), 5.65 (2H, s, COD-CH), 4.14 (5H, s, C5H5), 4.12 (5H, s, C5H5), 2.62 (4H, m, COD-CH2), 1.79 (4H, s, COD-CH2), other signals could not be assigned properly;
13

C NMR (CDCl3)

170.41, 84.58, 75.63, 73.74, 73.90, 73.33, 70.04, 69.96, 69.78, 66.46, 58.02, 29.29, 28.73; IR (KBr) 3101, 3013, 2926, 2882, 2838, 1620, 1454, 1436, 1414, 1375, 1331, 1256, 1146, 1103, 1046, 1002, 967, 830, 624, 506, 483; m/z (FAB) 693 ([M+ +2], 9%) 691 ([M+], 65%), 581 (7%), 495 (4%), 481 (6%), 396 (5%), 345 (3%), 307 (21%), 289 (20%), 233 (7%), 154 (100%). Anal. Calc. for C34H40N2Fe2Rh: C, 51.64; H, 5.10; N, 3.54; MW, 691.09454. Found: C, 51.46, H, 5.43; N, 3.31; MW, 690.7.

The tendency for the C and N content to be too low and H too high could be due to the presence of traces of water. This also applies to compounds [3.3]-[3.8].

99

3.5.2 Rhodium(I) complexes containing bisferrocenylamines3 3.5.2.1 Complex [3.4]

Silver tetrafluoroborate [3.0] (33.3 mg, 0.171 mmol) in acetone 2 cm3 was added to a solution of [Rh(COD)Cl]2 (42.1 mg, 0.086 mmol) in acetone (25 cm3) and the reaction mixture stirred
Fe

H N C H2

(CH2) Rh

H N C H2 Fe

BF4

vigorously at room temperature for a few minutes. The precipitated AgCl was filtered off and the yellow filtrate was stirred with N,N-ethylenebis(ferrocenylmethyl)amine (78.1 mg, 0.171 mmol) in acetone (20 cm3). The reaction mixture was left to stir at room temperature for 24 h. Reduction of the solvent volume and addition of hexane caused the precipitation of complex [3.4] as a yellow solid. After filtration, the solid was washed with diethyl ether and recrystallized from a dichloromethane/hexane mixture (85.4 mg, 66.2%). M.p. 182 (decomp.); IR (KBr) 3268, 3101, 2934, 2881, C 2829, 1638, 1454, 1410, 1383, 1335, 1304, 1234, 1107, 1085, 1028, 1002, 918, 822, 484; Anal. Calc. for C32H40N2Fe2Rh: C, 50.97, H; 5.35; N, 3.71. Found: C, 49.60, H, 6.01; N, 3.24.
3.5.2.2 Complex [3.5]

The procedure as for [3.4] was followed using silver tetrafluoroborate (23.2 mg, 0.122 mmol), [Rh(COD)Cl]2 (30.1 mg, 0.061 mmol) and N,Npropylenebis(ferrocenylmethyl)amine (55.8 mg,
Fe C H2

H N

(CH2) Rh

H N C H2 Fe

BF4

0.122 mmol). Complex [3.5] was obtained as a yellow solid (94.3 mg, 81.8%). M.p. 134 (decomp.); IR (KBr) 3271, 3092, 2937, 2888, 2831, 1633, 1454, 1381, 1332, C 1283, 1238, 1124, 1108, 1084, 1039, 1002, 974, 913, 819, 481; Anal. Calc. for C33H42N2Fe2Rh: 51.60, H, 5.51, N, 3.65. Found: C, 50.40; H, 5.66; N, 3.30.

No MS data was obtained for compounds [3.4]-[3.8] owing to a spectrometer breakdown.

100

3.5.2.3 Complex [3.6]

The procedure as for [3.4] was followed using silver tetrafluoroborate (36.1 mg, 0.185 mmol), [Rh(COD)Cl]2 [3.0] (45.6 mg, 0.093 mmol) and N,N-butylenebis(ferrocenylmethyl)amine (89.6
Fe C H2

H N

(CH2) Rh

H N C H2 Fe

BF4

mg, 0.185 mmol). Complex [3.6] was obtained as a yellow solid (84.8 mg, 72.3 %). M.p. 204 C (decomp.); IR (KBr) 3285, 3259, 3180, 3092, 2996, 2926, 2882, 2829, 1642, 1476, 1432, 1410, 1379, 1331, 1230, 1125, 1107, 1085, 1037, 1028, 997, 953, 923, 817, 488; Anal. Calc. for C34H44N2Fe2Rh: C, 52.21; H, 5.67; N, 3.58. Found: C, 51.38; H, 6.33; N, 2.57.
3.5.2.4 Complex [3.7]

The procedure as for [3.4] was followed using silver tetrafluoroborate (29.2 mg, 0.150 mmol), [Rh(COD)Cl]2 [3.0] (37.0 mg, 0.075 mmol) and N,N-bis(2,5-dimethylbenzyl)ethane-1,2diamine (44.5 mg, 0.150 mmol). Complex [3.7] was obtained as a light yellow solid (53.8 mg, 60.4 %). M.p. 110 (decomp.); IR C (KBr) 3250, 2964, 2926, 2882, 2838, 1629, 1506, 1458, 1388, 1339, 1304. 1164, 1125, 1085, 1059, 1037, 958, 817, 765, 528, 483; m/z (FAB); Anal. Calc. for C28H40N2Rh: C, 56.58; H, 6.78; N, 4.71. Found: C, 55.52; H, 7.50; N, 3.87.
3.5.2.5 Complex [3.8]
H N C H2 (CH 2 ) Rh 2 H N C H2 BF 4

The procedure as for [3.4] was followed using silver tetrafluoroborate (27.2 mg, 0.139 mmol), [Rh(COD)Cl]2 (34.3 mg, 0.070 mmol) and N,Nbis(2,4,6-trimethylbenzyl)ethane-1,2-diamine (45.1 mg, 0.139 mmol). Complex [3.8] was
C H2

H N

(CH2) Rh

H N C H2 BF4

obtained as a light yellow solid (63.6 mg, 68.1%). M.p. 170 (decomp.); IR (KBr) C 3259, 2961, 2917, 2873, 2829, 1638, 1616, 1581, 1458, 1432, 1379, 1340, 1304,

101

1120, 1085, 1063, 1032, 896, 852, 769, 716, 633, 611, 519, 484; m/z (FAB); Anal. Calc. for C30H44N2Rh: C, 57.89; H, 7.13; N, 4.50. Found: C, 53.71; H, 6.89; N, 3.56.

3.6 References
1. W. P. Griffith, The Chemistry of the Rarer Platinum Metals, John Wiley & Sons, London 1967. 2. M. A. Garralda and L. Ibarlucea, J. Organomet. Chem., 311 (1986) 225. 3. S. I. Lee, S. C. Shim and T. J. Kim, J. Polym. Sci., Part A: Polymer Chem.,
34 (1996) 2377.

4. P. Pertici, F. D Arata and C. Rosini, J. Organomet. Chem., 515 (1996) 163. 5. G. R. Julius and S. Cronje, Helvetica Chim. Acta, 85 (2002) 3737. 6. J. J. Kim and H. Alper, Chem. Commun., (2005) 3059. 7. M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, T. E. Mller and A. Zapf, J. Organomet. Chem., 566 (1998) 277. 8. B. S. Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell, Vogels Textbook of Practical Organic Chemistry, Longmann Scientific and Technical, England (5th Ed.) 1989. 9. Z. Otwinowski and W. Minor in C. W. Carter, J. Sweet and R. M. Sweet (Eds), Macromolecular Crystallography Part A, Academic Press, New York, 276 (1997) 307. 10. G. M. Sheldrick, SHELX97, Programme for Solving Crystal Structures, University of Gttingen, Germany, 1997. 11. G. M. Sheldrick, SHELX97, Programme for the Refinement of Crystal Structures, University of Gttingen, Germany, 1997. 12. L. J. Barbour, X-Seed, University of Missouri-Columbia, USA, 1999.

102

CHAPTER 4
RESULTS AND DISCUSSION

4.1 Polymerization of phenylacetylene

4.1.1 Introduction

Polyphenylacetylene (PPA) has been found to be a very interesting polymer because of its photoconductivity,1 photoluminescence,2 non-linear optical3 and membrane properties.4 Cametti et al.5 have also investigated iodine-doped polyphenylacetylene for potential application in technology. Polymerization of phenylacetylene has been carried out in various conditions, including cationic, radical and coordination mechanisms.6 Transition metal complexes have been used since the early pioneering work during 1930 to the 1950s. Masuda et al.7 first polymerized phenylacetylene in 1974 using WCl6 and MoCl5 as catalysts, to give high molecular weight polymers. Since then, other transition metal complexes (palladium, rhodium, iridium, etc) have been investigated for catalytic activity towards polymerization of polyphenylacetylene. The zwitterion complex Rh+(COD)BPh4- has been found to produce stereoregular cis-PPA with molecular weights up to 35 000, under hydrosilation conditions.8 The [Rh(norbonadiene)Cl]2 complex has, so far, been reported to yield the highest molecular weight of approximately 4.3 x 106.9 The catalytic activity of Rh(I), Ir(I) and Ru(IV) complexes containing 1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene and 1,3-di(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene ligands has been reported by Zhang et al.10 Molecular weights ranging between 55 000 and 200 000 have been obtained in ionic liquids using Rh(I) complexes as catalysts.11

103

4.1.2 Polymer characterization

Four possible stereoisomers can be formed in the catalytic polymerization of phenylacetylene (Figure 4.1).10 The stereochemistry of PPA can be generated from the configuration of the C=C bond and the conformation of C-C single bond of the polymer main chain. The stereoisomers can be easily distinguished by their physicochemical and spectroscopic properties.6
Ph H Ph H H Ph Ph Ph H Ph H H Ph H

cis-cisoidal

cis-transoidal

Ph

H Ph

Ph

Ph

Ph

Ph

H Ph

H Ph

trans-transoidal

trans-cisoidal

Figure 4.1: Stereoisomers of polyphenylacetylene

The solubility of the isomers can also be utilized as an aid to distinguish between them. For example, cis-transoidal and trans-cisoidal isomers are both highly soluble in benzene, while the cis-cisoidal isomer is insoluble. NMR and IR spectroscopy show that the cis-cisoidal and cis-transoidal isomers have similar spectroscopic behaviour, which differentiates them from the trans-cisoidal isomer. The most significant difference in the IR spectra of the three isomers is the presence of a band at 740 cm-1 in the cis-cisoidal and cis-transoidal isomers. This band represents the out-of-plane stretching of the C-H bonds and can also be associated with the cis content in the polymer. The trans-cisoidal isomer exhibits a band at 1265 cm-1 due to the out-of-plane deformation vibrations of the trans-C-H bonds. The band at 740 cm-1, present in the cis-cisoidal and cis-transoidal isomers, is lacking in the trans-cisoidal isomer. On the other hand, the band at 1265 cm-1, present in the trans104

cisoidal isomer, is lacking in the cis-cisoidal and cis-transoidal isomers. Hence, the band at 740 cm-1 can be used as a function of the cis content in the polymer and the band at 1265 cm-1 as a function of the trans content. The ratio between the bands at 1500 and 1450 cm-1 provides information about the stereochemistry of the polymer. A polymer with a cis content can be identified by a ratio of 1 or smaller, together with a strong band at 740 cm-1. A ratio greater than 1 and a band at 1265 cm-1 can be related to a polymer with a trans content. Some polymers with cis conformation can isomerise to trans conformation, resulting to ratios greater than 1 and weak bands at 740 cm-1.
1

H NMR spectra of the polymer have been used to differentiate between the

respective isomers by looking at differences in the chemical shifts of the aromatic protons. Apart from these differences, a signal at approximately 5.82 ppm represents the olefinic proton in the cis-cisoidal and cis-transoidal isomers. The trans-cisoidal isomer exhibits a smaller or no signal at 5.82 ppm and also displays a broad weak signal in the region 3-4 ppm due to the aliphatic protons. The area of the signal at 5.82 ppm can be correlared with the intensity of the band at 740 cm-1 to determine the cis content in the polymer.

4.2 Catalytic polymerization studies

The catalytic polymerization of phenylacetylene was studied with the complexes
[3.1], [3.2] and [3.3] (Table 4.1).

Ph

Catalyst, MeOH RT, 24 h Ph H n

Scheme 4.1: Polymerization of phenylacetylene with Rh(I) catalysts

105

Table 4.1: Polymerization of phenylacetylene with Rh(I) complexes.a Catalyst [3.1] [3.2] [3.3]
a b

Mn

Mw

Mw/Mn

cis-Content (%)b 98.7 100 99.4

8129 8223 8749

21203 21105 22330

2.6 2.6 2.5

Reaction conditions: 0.3 mol % catalyst in MeOH (15 cm3); at RT for 24 h Calculated according to reference 12 and 13

The aim was to determine the effect, if any, of increasing the length of the alkylene chain of the bidentate nitrogen-donor ligands on the catalytic activity of the complexes. The number average molecular weight Mn, weighted average molecular weight Mw, polydispersity index (Mw/Mn) and the cis-content of the polymer samples were determined (Table 4.1). The molecular weights Mw of the polyphenylacetylene obtained for all the catalyst were similar, but they were approximately 4 times smaller than the literature values for similar types of complexes (Table 4.1). For example,
[3.1] has been investigated for its catalytic activity in the polymerization of

phenylacetylene and was found to have the highest catalytic activity with a molecular weight of approximately 86 000.6 However, according to the results in Table 4.1,
[3.3] produced the highest molecular weight polymer. Moreover, since there was not

much of a difference between the molecular weights and the fact that the molecular weight decreased from [3.1] to [3.2], it was very difficult to conclude on the influence of increasing the length of the alkylene chain. The lower polydispersity values (~2.5) that were obtained imply a more uniform distribution of the polymers.6 All the catalysts that were investigated resulted in polymers with high a cis content (Table 4.1). Complex [3.2] produced a polymer with the highest cis content.

4.2.1 Spectroscopic properties of polymers

As already mentioned, the stereochemistry of the isomers can be deduced from the physicochemical and spectroscopic properties. All the catalysts that were investigated produced polymers with similar 1H NMR and IR spectra. All spectra 106

exhibited a signal at 5.86 ppm, due to olefinic protons, which was indicative of cisisomer polymers (Figure 4.2). Two further signals at 6.96 and 6.65 ppm were due to the aromatic protons. According to the literature, the pattern of the signals indicates a stereoregular polyphenylacetylene with a predominantly cis-transoidal structure.14 The insolubility of the polymer in methanol made its separation very easy.

Figure 4.2: 1H NMR spectrum of PPA, catalyzed by [3.2]

Infrared spectra of the polymers that were prepared exhibited a strong absorption band at max 737 cm-1 and lacked the absorption band at max 1265 cm-1 (Figure 4.3). This information confirmed a cis-isomer polymer and that the polymers produced were linear.14 The ratio of the infrared absorption band at max 1500 and 1450 cm-1 can provide information about the stereochemistry of the polymer. A ratio of 1 or smaller, together with a band at max 740 cm-1 indicates the cis content, while a ratio greater than 1 and a band at max 1265 cm-1 indicates the existence of trans content of the polymer.

107

wavenumber (cm )

-1

Figure 4.3: IR spectrum of PPA prepared using [3.2]

As shown in Figure 4.3, all polymers produced absorption bands at max 1488 and 1443 cm-1 (Figure 4.3). Ratios of approximately 1.00 were calculated for these bands and all were consistent with the cis content of the polymer (Table 4.2).
Table 4.2: Determination of cis-content of polymers Catalyst Band Ratio (1488 vs 1443) [3.1] [3.2] [3.3]

cis-Content (%) 98.7 100 99.4

Polymer Colour

1.05 1.03 1.02

Yellow Yellow Yellow

4.2.2 Thermal analysis

The TGA curve showed that the polymer was stable up to 260 in a nitrogen C atmosphere (Figure 4.4). Decomposition of the polymer continued slowly as the temperature increased until a residue of 7% remained, at 475 C.

108

Figure 4.4: TGA and DSC curves of PPA obtained with [3.1]

The DSC thermogram displayed peaks associated with the cis content of the polymer and no glass transition was observed. Two exothermic peaks at 172 and 250 were observed. The two peaks corresponded to the cis-trans isomerization C and the crystallization phenomena, respectively.15 An endothermic peak occurred at 300 which corresponded to thermal decomposition of the polymer. C

4.2.3 Mechanistic pathways for polymerization of phenylacetylene

The transition metal catalyzed polymerization of phenylacetylene is widely known to occur via two main mechanisms: the four-centre acetylene insertion mechanism (insertion mechanism)16 and metallacycle (or metathesis) mechanism.17 The first step of the insertion mechanism is the displacement of the cyclooctadiene in the catalyst precursor by the solvent, leading to the formation of the species [Rh(NN)(solvent)2]+ in solution. The formation of a hydridoacetylenic species follows via the oxidative addition of phenylacetylene to the rhodium(I) metal centre. The coordination is followed by a migratory insertion, resulting in the formation of a vinylic rhodium intermediate species, consequently resulting in the formation of the polymer (Scheme 4.1).

109

Ph C M C

H * HC P * CH H C *

Ph C M C * H C

P = polymer chain M = Rh H C M H C C * C * H H H C H C P

H H C * C *

P C H

C H

Scheme 4.2: Insertion mechanism for polymerization of phenylacetylene16,18

The metallacycle occurs via the formation of a metal-carbene complex with a vinylic metallacycle intermediate. A key step is the rearrangement of a monomer unit formed by the stepwise addition of a second metal-carbene complex. The polymer is formed by the repetition of the above steps (Scheme 4.2).
H M P C H P = polymer chain M = Rh C* C* H

M C P H

* HC

* CH

P H P C H C C* * H C C H M H H HC CH C * M C C *

Scheme 4.3: Metallacyclic (metathesis) mechanism for the polymerization of

phenylacetylene19

110

An apparent distinction between the two mechanisms is that the insertion mechanism predicts that two carbons of a monomer unit become doubly bonded to each other, while the metallacycle mechanism predicts that two carbons of a monomer unit end up singly bonded to one another in the resulting polymer.20 However, it is generally believed that the polymerization of acetylene catalyzed by rhodium complexes proceeds via the insertion mechanism, resulting in stereoregular polymers.

4.3 Hydroformylation of styrene

4.3.1 Introduction

The hydroformylation or oxo reaction was discovered by Otto Roelen in 1938, through modification of the Fischer-Tropsch synthesis to produce aldehydes and ketones rather than hydrocarbons as the main products.21-23 He observed that ethylene, H2 and CO were converted into propanal and diethyl ketone (high pressures) in the presence of Co2(CO)8 as a catalyst. However, aldehydes are the primary products of the hydroformylation of olefins or alkenes (Scheme 4.3).
CHO H 2 , CO R Catalyst R linear CHO + R

branched

Scheme 4.4: Hydroformylation of olefins

Hydroformylation reactions are very important industrial processes in that most aldehydes (linear) produced can be reduced to alcohols or oxidized to carboxylic acids.23 Alcohols are used for the synthesis of phthalate plasticizers by esterification reaction with phthalic anhydride. In turn, the phthalate plasticizers are used primarily for polyvinyl chloride plastics. The aldehydes are also used for the production of detergents, surfactants, solvents, lubricants, cosmetics and other widespread chemicals.23,24 Branched aldehydes are also very useful for stereoselective and asymmetric synthesis.24 Thus, hydroformylation reactions have attracted more attention from both industrial and academic research groups. 111

Until the early 1970s, cobalt carbonyl complexes were the most employed homogeneous catalysts in the hydroformylation of alkenes.21,23 The dimeric dicobaltoctacarbonyl complex Co2(CO)8 was believed to be rapidly converted into a cobalt hydrocarbonyl species HCo(CO)4, by H2/CO under pressure and was the active species in the hydroformylation of alkenes. However, the regioselectivity of the HCo(CO)4 towards linear aldehydes depends on the reaction conditions and the alkene substrate used. Modification of the HCo(CO)4 catalyst by replacing one carbonyl ligand with a trialkylphosphine PR3 to produce HCo(CO)3(PR3), led to an improvement in the rate of reaction and regioselectivity.25 The replacement of the CO ligand with trialkylphosphine causes stronger Co-CO bonding and consequently decreases the CO partial pressure, thereby stabilizing the catalyst. It also prevents the formation of Co metal. The success of rhodium catalysts led to a decrease in the use of cobalt carbonyl catalysts. The reason was mainly because rhodium catalysts were more catalytically active than cobalt catalysts. The use of rhodium carbonyl complexes favoured formation of a higher proportion of linear aldehydes at comparable temperatures. Hydroformylation of alkenes26 and alkynes27 using tris(triphenylphosphine)chlororhodium as a catalyst have been achieved by Osborn et al.26,27 Union Carbide developed a ligand BIPHEPHOS, which in conjunction with Rh(CO)2(acac), resulted in regioselective formation of linear aldehydes from various functionalized terminal alkenes under mild conditions (Scheme 4.4). The aldehyde was then converted to the indolizidine alkaloid. Many rhodium complexes have been employed as catalysts for hydroformylation reactions and examples can be obtained in the review article of Clarke.24

112

N BOC

CO

H2

Rh(CO)2 (acac) BIPHEPHOS 60 C, 5 atm, 83% N BOC

CHO

MeO

OMe

Bu

Bu

BIPHEPHOS =

P O

O P O

Scheme 4.5: Synthesis of precursor to the indolizidine alkaloid

4.3.2 Catalytic hydroformylation studies

The catalytic activity of the rhodium(I) complexes was investigated for the hydroformylation of styrene. Scheme 4.5 illustrates the possible aldehydes expected from the hydroformylation of styrene, that is, 2-phenylpropanal (branched) and 3phenylpropanal (linear).
CHO CHO + CO + H2 catalyst 800 psi, 20 h 2-phenylpropanal 3-phenylpropanal +

Scheme 4.6: Hydroformylation of styrene catalyzed by [3.4]-[3.8]

The two products and unreacted styrene were identified and distinguished by 1H NMR spectroscopy. 2-Phenylpropanal was identified by a high intensity doublet at 9.72 ppm due to the CH=O group, a a doublet of quartets at 3.67 ppm due to the -proton and a high intensity doublet at 1.48 ppm due to the methyl group (Figure 4.5). 3-Phenylpropanal exhibited very low intensity signals, a triplet at 9.84 ppm due to the CH=O group and two triplets at 2.99 and 2.81 ppm due to the - and CH2 groups, respectively. Unreacted styrene was identified by a doublet of doublets at 6.76 ppm due to the vinylic CH group and two doublets at 5.80 and 5.31 ppm due to the cis- and trans-protons of the vinylic CH2 group. 113

Figure 4.5:

H NMR spectrum of the products of hydroformylation of styrene catalyzed by [3.6]

All complexes [3.4]-[3.8] exhibited excellent catalytic activity and selectivity towards the hydroformylation of styrene (Table 4.3). Conversions of styrene were comparable; however, [3.8] resulted in the highest conversion of styrene. All complexes selectively favoured the formation of the branched aldehyde, 2phenylpropanal. It has been shown that the bite angle of chelating ligands have a direct effect on the regioselectivity of hydroformylation reactions.28 Chelating ligands with bite angles greater than 90 favour linear over branched aldehydes. Complexes
[3.4]-[3.8] are expected to be in a square planar configuration, and thus would have

bite angles of approximately 90 which explains why all compounds favoured , branched over linear aldehydes. Complexes [3.7] and [3.8] provided excellent yields with [3.8] recording the highest yield of all the complexes. Complexes [3.4]-[3.6] provided excellent conversion of styrene and selectivity towards branched aldehydes, however, the yields were moderate. The reason was thought to probably be that the aldehyde formed was further hydrogenated to an alcohol or that the styrene was hydrogenated to ethylbenzene. In addition, the GC chromatograms of
[3.5] and [3.6] showed an extra peak before 13 minutes and after 17 minutes,

114

respectively. These peaks were not observed in any of the other chromatograms. However, the side products were not isolated from the reaction mixture.
Table 4.3: Hydroformylation of styrene catalyzed by rhodium(I) complexes Entry Catalyst Conversionb (%) Selectivity B/L Ratioc Yield (%)d 2-PP 3-PP

1 2 3 4 5
a

[3.4] [3.5] [3.6] [3.7] [3.8]

90 92 89 95 99

27 25 26 27 25
3

74 70 69 91 95

2.4 2.7 1.9 1.8 1.8

Reaction conditions: cat. (10 mg), toluene (150 cm ), CO/H2 (400/400 psi), alkene/cat. ratio (1000),

RT, 20h. bDetermined by GC. cDetermined by 1H NMR and GC. dDetermined by GC.

Kim and Alper have reported that sterically hindered rhodium catalysts resulted in low conversions of styrene.29 This effect was due to the bulkiness of the chelating nitrogen donor ligands in the rhodium catalysts. The presence of the bulky ferrocenyl substituents on the chelating ligands in [3.4]-[3.8] explains the reason for the lower conversions, compared to the smaller benzene substituents on the ligands in [3.7] and [3.8]. In conclusion, [3.7] and [3.8] gave the best results since both recorded high conversions of styrene and excellent aldehyde yields.

4.3.3 Mechanism for hydroformylation of styrene

The mechanism for the hydroformylation of styrene is proposed here although it was not investigated in this project. It is well documented that the COD ligand is readily replaced by the carbonyl ligand even at room temperature.29,30 Therefore, it has been suggested that in the presence of CO and H2, the COD in the rhodium catalyst is replaced by CO, resulting in the pentacoordinated reaction rhodium pathways species for the RhH(NN)(CO)2. The RhH(NN)(CO)2 is believed to be active in the hydroformylation reaction. Scheme 4.6 illustrates the possible hydroformylation of styrene.

115

N Rh N

+ CO H2

H N CO Rh N CO N Ph N

Ph

N Rh

Ph

Rh CO CO N

CO CO

less favoured CO

Ph N Rh N CO N H N Rh CO

CO highly favoured

CHO Ph

H H2

N Rh C O Ph N

O C

Ph

Rh N CO

CO

Scheme 4.7: Possible mechanism for hydroformylation of styrene catalyzed by [3.4][3.8]

The mechanism is also thought to occur in an analogous manner as the one proposed by Wilkinson.30 The initial step involves the addition of styrene to the RhH(NN)(CO)2 species, followed by the insertion of styrene resulting in the rhodium alkyl complex that undergoes migratory insertion of CO to form the rhodium acyl complex. This step is followed by the oxidative addition of H2 to give the dihydrido acyl rhodium complex. This step is rate determining and is the only one that results in the change in oxidation state of the rhodium. The final step involves the reductive elimination of the product and the reformation of the active rhodium hydride species.

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4.4 Experimental
4.4.1 Purification procedures

All solvents used were purified and dried as in the previous Chapters. Phenylacetylene and styrene were obtained from the Sigma Aldrich Chemical Company, Milwaukee, USA. The synthetic gases H2 and CO were obtained locally from Afrox.

4.4.2 Instumentation

Gel Permeation Chromatography was conducted at the Stellenbosch University with a Waters 717 autosampler, a Waters 619 flow unit, a Waters 410 difractometer, a Waters 600E system controller, a Waters 515 HPLC pump, a Valveco 8-port switch for high and low temperature HPLC applications and a Wyatt technology laser photometer. The programme was controlled using a MilleniumTM software. Gas Chromatography was conducted on a Focus GC Thermo Finnigan instrument (Model no: AI 3000) equipped with a flame ionization detector (FID) and a DB 1701 column (film thickness 0.25 m, internal diameter 0.25 mm, length 30 m). The Delta Chromatography software was used for recording and integration of chromatograms.

4.4.3 Polymerization of phenylacetylene6

Polymerization of phenylacetylene was carried out in a 2-necked round-bottomed flask (25 cm3) under an argon atmosphere using Schlenk techniques. The catalyst (0.02 mmol) was added to a solution of phenylacetylene (0.55 g, 5.44 mmol) in methanol (15 cm3). The reaction mixture was stirred at RT for 24 h. The yellow precipitates which formed were filtered off, washed with methanol and then dried under the vacuum. The polymers were analysed by NMR and IR spectroscopy, thermal analysis and gel permeation chromatography.

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4.4.4 Hydroformylation of styrene29

All hydroformylation reactions were conducted in a 2 L Parr stirred reactor. The reactor was charged with an appropriate amount of styrene (1000 equiv.), catalyst (10 mg) and toluene (150 ml). The reactor was flushed three times with CO and pressurized to 400 psi. After attaching and purging of the H2 line, the reactor was pressurized to 800 psi. After stirring the reaction for 16 h, the excess CO and H2 were released. The reaction mixture was analysed with 1H NMR and GC. Similar conditions were used for hydroformylation reactions 4.4.4.1-4.4.4.5.
4.4.4.1

Hydroformylation of styrene (1381 mg, 13.26 mmol) with [3.4] (10 mg, Hydroformylation of styrene (1356 mg, 13.02 mmol) with [3.5] (10 mg, Hydroformylation of styrene (1332 mg, 12.79 mmol), with [3.6] (10 mg, Hydroformylation of styrene (1753 mg, 16.83 mmol) with [3.7] (10 mg, Hydroformylation of styrene (1674 mg, 16.07 mmol) with [3.8] (10 mg,

0.01326 mmol). Conversion: 90%.

4.4.4.2

0.01302 mmol). Conversion: 92%.

4.4.4.3

0.01279 mmol). Conversion: 89%.

4.4.4.4

0.01683 mmol). Conversion: 92%.

4.4.4.5

0.01607 mmol). Conversion: 95%.

4.5 References
1. E. T. Kang, K. G. Neoh, T. M. Masuda, T. Higashimura and M. Yamamoto, Polymer, 30 (1989) 1328. 2. C. W. Lee, K. S. Wong, W. Y. Lam and B. Z. Tang, Chem. Phys. Lett., 307 (1999) 67. 3. D. Neher, A. Wolf, C. Bubeck and G. Wegner, Chem. Phys. Lett., 163 (1989) 6705. 4. T. Kaneko, T. Yamamoto, H. Tatsumi, T. Aoki and E. Oikawa, Polymer, 41 (2000) 4437. 5. C. Cametti, A. Furlani, M. V. Russo and G. Lucci, Synth. Met., 83 (1996) 77.

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6. S. I. Lee, S. C. Shim and T. J. Kim, J. Polym. Sci. A: Polymer Chemistry,

34 (1996) 2377.

7. T. Masuda, K. Hasegawa and T. Higashimura, Macromolecules, 7 (1974) 728. 8. Y. Goldberg and H. Alper, Chem. Commun., (1994) 1209. 9. M. Tabata, W. Yang and K. Yokoda, Polym. J., 20 (1990) 1105. 10. Y. Zhang, D. Wang, K. Wurst and M. K. Buchmeiser, J. Organomet. Chem.,
690 (2005) 5728.

11. P. Mastrorilli, C. F. Nobile, V. Gallo, G. Suranna and G. Farinola, J. Mol. Catal. A: Chemical, 184 (2002) 73. 12. C. I. Simionescu, V. Percec and S. Dimitrescu, J. Polym. Sci. Polym. Chem. Ed., 15 (1977) 2497. 13. A. Furlani, S. Licoccia, M. V. Russo, A. Camus and N. Marsich, J. Polym. Sci. A: Polym. Chem., 24 (1986) 991. 14. I. M. Barkalov, A. A. Berlin, V. I, Goldanskii and G. Mingao, Vysokomol. Soedin., 5 (1963) 368. 15. F. D. Kleist and N. R. Byrd, J. Polym. Sci. A-1, 7 (1969) 3419. 16. S. Shirakawa and S. Ikeda, J. Polym. Sci. Chem. Ed., 12 (1974) 929. 17. T. Masuda and T. Higashimura, Adv. Polym. Sci., 81 (1986) 121. 18. G. Wegner, Angew. Chem. Intl. Ed. Engl., 20 (1981) 361. 19. C. C. Han and T. J. Katz, Organometallics, 4 (1985) 2186. 20. C. S. Yannoni and R. D. Kendrick, J. Chem. Phys., 74 (1981) 747. 21. M. M. T. Khan and A. E. Martell, Homogeneous Catalysis by Metal Complexes, Academic Press, Inc., New York, 1974. 22. J. Tsuji, Transition Metal Reagents and Catalysis: Innovations in Organic Synthesis, John Wiley & Sons, LTD, New York, 2000. 23. http:/ hydroformylation.doc. 24. M. L. Clarke, Current Organic Chemistry, 9 (2005) 701. 25. L. H. Slaugh and D. Mullineaux, J. Organomet. Chem., 13 (1968) 469. 26. J. A. Osborn, F. H. Jardine, J. F. Young and G. Wilkinson, J. Chem. Soc. A. (1965) 1711. 27. F. H. Jardine, J. A Osborn, G. Wilkinson and J. F. Young, Chem. Ind. (London), (1965) 560. chemistry.Isu.edu/Stanley/webpub/4571-Notes/Chap16-

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28. C. P. Casey, G. T. Whiteker, M. G. Melville, L. M. Petrovich, J. A. Gavney, Jr. and D. R. Powell, J. Am. Chem. Soc., 114 (1992) 5535. 29. J. J. Kim and H. Alper, Chem. Commun., (2005) 3059. 30. C. K. Brown and G. Wilkinson, J. Chem. Soc. A, (1970) 2753. 31. W. Klui, D Schramm and G. Schramm, Inorg. Chim. Acta, 357 (2004) 1642.

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CHAPTER 5 CONCLUSION

5.1 Conclusion
Bisferrocenylimines and arylbisimines were successfully prepared under solvent-free conditions and were fully characterized. The solvent-free reactions carried more advantages than the solvent reactions, and these included shorter reaction times, better yields and required no heat. The reduction of the above compounds was achieved by lithium aluminium hydride (LAH). Cationic rhodium(I) complexes containing bisferrocenylimines were successfully prepared and fully characterized. Suitable single crystals grown allowed the determination of the structures of [3.2] and [3.3] using X-ray crystallography. The successful only synthesis of cationic rhodium(I) spectroscopy, complexes cyclic containing bisferrocenylamines and arylbisamines was also achieved. Characterization was possible with IR and UV-vis voltammetry and conductometry. For example, UV-vis spectra of [3.1], [3.2] and [3.3] showed an extra band at max 350, 382 and 383 nm, respectively compared to the corresponding free ligands [2.1], 2.2], and [2.3]. The bands that also appeared in the free ligands were shifted to higher wavelengths. Similarly, [3.4], [3.5], [3.6], [3.7] and [3.8] exhibited bands at max 385, 388, 387, 382 and 381 nm. All these bands were attributed to coordination of the ligands to the rhodium(I) ion. Complexes [3.1], [3.2] and [3.3] were catalytically active in the polymerization of phenylacetylene. The molecular weights of the polymers were very low, with Mw = 22330 being the highest molecular weight recorded for [3.3]. All polymers produced with the catalysts were in the cis-transoidal configuration. Complexes [3.4]-[3.8] were catalytically active in the hydroformylation of styrene. All complexes favoured the formation of the branched (iso) aldehyde 2-phenylpropanal. Complexes [3.7] and
[3.8] were most active catalysts with the highest conversions of styrene.

121