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(FINAL) CHEMISTRY
BLOCK-I
1
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
BLOCK – I : SUMMARY
2
UNIT-1 ALKYLS AND ARYLS OF TRANSITION METALS
STRUCTURE
1.1 Introduction
1.2 Objectives
1.3.1 Nomenclature
1.3.4 Stability
3
1.1 INTRODUCTION
4
1.2 OBJECTIVES
The main objective of this unit is to give all the necessary information
about alkyl and aryl compounds of transition metals. After going through this
unit you should be able to :
know what are metal-alkyls and metal-aryls,
understand how they are named,
describe classification and types of alkyls and aryls of transition metals,.
discuss methods of synthesis of hydrocarbyls of different groups of
transition metals.
explain stability, decomposition pathway, and characteristic reactions of
transition metal-hydrocarbyls, and
discuss the importance of organo-copper compounds in organic-
synthesis.
Compounds of metals with alkyl radicals are called 'metal alkyls', while
those with aryl radicals are known 'Metal aryls'.
Although (Me3 PtI)4 was synthesised in 1907, but for a long time it was
considered that the bonded transition metal alkyl and aryls tend to be rather
unstable compared to their main group analogues. This inference was drawn
from the fact, diethyl iron (II) and diethyl cobalt (II) could not be prepared by
the action of metal bromide with ethyl magnesium bromide. As a matter of fact
metal-carbon bond in transition metal alkyls is not less stable compared to that
present in main group metal alkyls. But, while in main groups M-C bond-
strength regularly decreases, the bond strength gradually increases with increase
5
in atomic number. (Table 1.1). In this respect, the compounds of first transition
metal series will be least stable thermodynamically. As a matter of the difficulty
in making metal-carbon bond, is not due to thermodynamic but due to kinetic
aspect. Which makes their synthesis difficult.
Table 1.1
Enthalpies, D KJ mol-1 of Metal Carbon bond Dicomposition
Complex Enthalpy
Ti (CH2 CMe3)4 198
Zr (CH2 CMe3)4 249
Hf (CH2 CMe3)4 266
(CO)5 Mn Me 187
(CO)5 Re Me 220
1.3.1 Nomenclature
Based on Werner's and IUPAC rules of naming organometallic
compounds, names of Zn (C2 H5)2 will be diethyl zinc (II) and that of [Me3 Pt
Cl], Chloro trimethyl Platinum (IV), i.e. names of metal-alkyls and metal-aryls
6
may be derieved after naming the ligands in alphabatic order, name of the metal
follows with oxidation state in paranthesis.
7
Stable bonded covalent organometallic compounds are generally
formed by metals having 18 electrons or nearly 18 electrons – subshell (d-block
metals of group 11 and 12, and p-block metals of group 13 to 16), while
bonded organometallics of transition metals of with incomplete d-orbitals
are generally unstable.
Homoleptic, MRn, are those metal hydrocarbyls in which all the organic
groups on the metal atom are the same e.g. Ti Me4, [Ti {CH (SiMe3)2}3]
and [V Ph6] etc.
8
(b) On the basis of nature of ligands, these are classified into 'Alkyl
Organometallics' or 'Aryl Organometallics'. Organometallics with alkyl
radicals are called metal alkyls, eg. Ti (Me)4, Hf (CH2 But)4, WMe6 etc.
Similarly, organometallics with aryl radicals are designated as metalaryls,
e.g. (Sc (Ph)3, [La Ph4]-, [V (Ph)6]4-, Hf (CH2 Ph)4 etc.
9
Fig. 1.1 : Bi-and Poly nuclear Hydrocarbyls
various transition metals have been synthesised using the alkyl radicals
having no hydrogen (eg. Ph CH2 CH3, CH3 C (CH3)3 etc.). The most
important example of this method is the synthesis of metal methyls, M
(CH3)n of different metals. On the same basis stability of metal benzyls
[M (CH2 C6 H5)n ] and metal neopentyls. [M (CH2 C6H5)3]n] may be
explained.
10
the analogous neopentyls M(CH2CMe3)n. This can be understood as the
substitution of carbon atom in the ligand by silicon precludes the
possibility of hydrogen elimination as the formation of C = si
analogue of the alkene is very unlikely. Some other examples of ligands
of this type can be cited as –CH2GeR3 and –CH2SnR3 as well as
1-norbornyl in which case also the resulting bridge head alkene is highly
unstable). the cause of high stability is the fact that silicon, germanium
and tin have no tendency for formation of hydroalkene.
H....M
H
R' - C = C
H
R"
in which the coordination number of the metal has been increased. It,
therefore, follows that if the coordination sites of the metal were already
saturated by the presence of other ligands on the metal, then the
formation of the complex (B) would be precluded. A few examples of
derivatives of this type stabilized by the presence of the other ligands are
: Mo (CH2 CH3)(CO)3( 5-X5H5); Mn(CH2CH3) (CO)5: and Fe ( 5-X5H5)
(CO)2( 5-X5H5). Such stabilizing ligands are generally bonding or
acid type, but could also be other Lewis bases like ammonia in [Rh
11
(C2H5)(NH3)5]CIO4)2 or bissalicylaldehyde-ethylenediimine (salen) in
(Co(C2H5) salen)].
12
form polynuclear one also) in their 3, 4, 6 and 8 oxidation states. (Table
1.2). The general methods used for their synthesis are (i) halide exchange
and (2) ylide synthesis :
13
6 (d2 sp3) [M Me6]3-,
M (-CH2)2 P Me2)3
(M – Lanthanide metal)
Actinides +4 4 (sp3) Th (CH2 Ph)4
6 (2 sp3) [U Me6]2-
[U (CH2 Si Me3)6 ]2-,
[U (Ph)6]2.
+5 8 Cubic [U (CH2 Si Me3)3]3.
(M = Lanthanide metal
(vii) UCl4 = 6Li Me
Solvent
Li2 [U Me6]. 8 Et2 O/THF
( Et 2 O / THF )
14
THF
(viii) ThCl4 + 4 Li CH2 Ph Th (CH2 Ph)4 + 4 Li Cl
LowTemp.
2. Ylide Synthesis
As has been shown, chelating ligands play important part in stabilization
of transition metal- alkyl bond. An important example of this is the use of
phosphorous ylide :
M = Lanthanide metal
1.3.3.2 Hydrocarbyls of Group-4 (d2 metals)
d2 – metals of group-4 in their +2, +3 and +4 oxidation states form
hydrocarbyls with coordination numbers 2, 3, 4, 5 and 6. Using the
ligands fulfilling stereochemical requirements, we generally get tri
coordinated alkyls (or aryls) which are stable at sufficient temperatures
(Table 1.3). Where as, Ti (iii) gives homoleptic compounds, Zr and Hf
form heteroleptic compounds. The methods used for synthesis of these
alkyls (or aryls) are (1) Halide exchange, (2) Transmetallation (3) Metal
hydride alkene insertion and (4) ylide synthesis :
Table 1.3 : Representative alkyls (or aryls) of group 4 Transition metals.
15
+3 3 (sp3) Ti (CH2 Si Me3)3;
Ti [CH (Si Me3)2]3;
Ti R ( 5 C5 H5)2'
(R = P, 2, 6 Me2 C6 H3; 2, 4, 6-
Me3 C6 H2 etc.)
+4 4 (dsp2) Ti Me2 (DMPE)2;
4 (sp3) Ti Me4; Ti Ph4
Ti (CH2 But)3
Ti (CH2 Si Me3) 4;
Ti Me3 (5 C 5 H5)
Ti Me3 Cl, Ti me Cl3
+3 5 (dsp3) Ti Cl2 R (Py)2
(R = Me, Ph.)
+4 5(dsp3) [Ti Me]5-
Zr +4 4 (sp3) Zr Me4, Zr Ph4;
Zr (C6 H5)4;
Zr (CH2 Ph)4;
Zr (CH2 But)4;
Zr (Ch2 (Si Me3)4;
Zr Cl {CH (Si Me3)2}3;
Zr Cl (Ph) ( 5-C5 H5)2
Hf +4 6 (d2 sp3) [Zr Me6]2-
+4 4 (sp3) Hf (CH2 But)4;
Hf (CH2 Ph)4;
Hf (CH2 Si Me3)4;
Hf Cl [CH (Si Me3)2]3
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(1) Halide Exchange
(i) M Cl4 + 4 Li Me
ROR
M (Me4) + 4 Li Cl
.80
(M = Ti Or Zr)
ROR
(ii) M Cl4 + 4 Mg (CH2 Ph) x M (CH 2 Ph) 4 4MgClx
60C
(M = Ti, Zr Or Hf)
(iii) M Cl4 + 4 Li CH2 Si Me3 M((CH 2 SiMe 3 ) 4 4LiCl
Et o 2
(M = Ti Zr Or Hf)
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Ti Cl4 + Pb R4 Ti Cl3 R + Pb (R)3 Cl
(R = Me Or Et)
(3) Metal Hydride Alkene Insertion
Zr (H) Cl ( 5 C5 H5)2 + Li Ph Zr (Cl) (Ph) ( 5 C5 H5)2 + Li H.
(4) Ylide Synthesis
Ti Cl4 + n Me3 P = CH2 Ti Cl4 (CH2 P Me3)n
(n = 2, 3)
Zr Cl4 + n Me3 P = CH2 Zr Cl4 (CH2 P Me3)n
(n = 2, 3)
M Cl2 ( 5 C5 H5)2 =2 Me2 P=CH2 [M (CH2 P Me3)2
5
C5 H5)2+ 2 Cl.
18
6 (d2sp3) V Ph3 (THF)3
+4 4 (dsp2) V Me4 VPH4,
V (CH2 SiMe3)4'
V (CH2 Ph)4;
Nb +4 4(sp3-) Nb (C6F5)4'
H
(Me3 (CH2)3 M= C
CMe3
+5 5(sp3-) Nb Me 5;
Nb Cl3, Me2;
Nb (CH2 SiMe2)2Cl3
6 (d2sp3) [Nb Ph6;]-
[Nb Me5 (dme) ]
Ta +5 5 (dsp3-) Ta Me5;
Ta (CH2 Ph)3'
Ta Cl2 Me3'
Ta Cl2 (CH2 SiMe3)3
6 (d2sp3) [Ta Ph6]-
Ta M5 (dme)
19
(v) VCl3 (THF)3+3 Mg X (2,4,6 – Me3 C6 H2) THF
,
3Mg X Cl + V
30º C
ROR
(viii) Nb Cl3 Me2 + 3 Li me + dMe Nb Me5 (dme) + 3 LiCl
80º C
Et 2 O
(ix) Ta Cl2 Me3 + 2 Li Me TaMe5 dme
TaMe5 (dme)
78º c
H
(x) MCl- (CH2 CMe3)3 + 2 Li CH2 CMe3 Pentone
(Me3 CCH2)2M= C
CMe3
+ 2 Li Cl + Me3 CCH3
(M = Nb or Ta)
(2) Trans Metallation
Weak alkylating agents react to give partial halide exchange resulting in
heteroleptic alkyls (or aryls) :
Nb Cl5 + ZnR2 Pen
tan
e NbCl3 R 2 ZnCl2
20
Table 1.5 : Hydrocarbyls of Group -6
Metal Oxidation Coordination Alkyl (or Aryl) compounds
State Number
(Hybridisation)
Cr +2 2 (dsp2) Trans - CrMe2 (dmpe)2
[Cr Me4]2-
6 (d2sp3) Cr2 Me8]4-
+3 3 (sp2) Cr (CH2Ph)3'
Cr [CH (SiMe3)2]3
4(sp3) [Cr Ph4].'
[Cr (CH2 (Si Me3)4]
[Cr2 (CH2 SiMe3)4 (PMe3)2]
6 (d2sp3) Cr RCl2 (THF)3
(R = Me, Et, Pr, But)
Cr Ph3 (THF)3,
Cr [(CH2)2 PMe2]3 t
+4 4 (sp3) Cr Me4 ; Cr Bu+4;
Cr Pr4 ; Cr (CH2 SiMe3)4;
Cr R4 (R=CH2 CMe3
CH2C(Ph) Me2, CH2 CPh3)
6 (d2sp3) [Cr Me6]2-
Mo +2 5 (d2sp3) Mo (CH2Ph) (CO)3 ( ' C5H5)
+3 6 (d2sp3) (Mo2 MeM)4-
+4 4 (sp3) Mo (CH2 Ph)4; Mo (Mes)4
Mesitylene
+5 6 (d2sp3) Mo2 R6
(R=CH2 Si Me3, CH2 C Me3)
21
W +3 6 (d2sp3) W2 Me82-
+4 4 (sp3) W (CH2Ph)4;
6 (d2sp3) W Ph62-
+5 5 (d2sp3) W (Ph)5
+6 6 (d2sp3) W Me6 ; W (R) Cl3
(R = Me, Ph, Et, But)
22
= Sn Et4 ((") R = Et
= Sn Bu4 ( ") R = Bu
= Sn Ph4 (") R = Ph.
(iii) Li4 [Mo2 Me8] + 4 Me4 PCl [Mo2 {(CH2)PMe2}4] + 4CH4 + 4 LiCl
(iv) react with metal chlorides to give spirocyclic derivatives : Ylide of
Phosphorous
23
Table 1.6 : Hydrocarbyls of Group-7
Metal Oxidatio Coordination Alkyl (or Aryl)
n State Number
Mn +1 6 (d2sp3) Mn (CF3) (CO)5;
Mn (CH3) (CO)5;
Mn [C(:O) CH3] (CO)5;
Mn [C (:O) Ph] (CO)4; (PPh3)
Mn [C6H4 Me] (CO)5
+2 4 (sp3) Mn Me2 (dmpe)2 ;
Mn Me42-, Mn (CH2 SiMe3)42-
[Mn{CH2C(Ph)Me2}2]2;
[Mn {CH2CMe3}2]2;
[Mn {CH2 Si Me3}2]2
+3 4 (sp3) [Mn (CH2CMe2PPh3)3]2
+4 4 (sp3) [Mn (CH2But)2]4
[Mn (CH2Si Me3) 2] n;
[Mn{C(Si Me3)3]2
Re +3 4 (sp3) Re2 ( Si Me3) 2 (CH2 Si Me3) 4
6 (d2sp3) Re2 Me82-
+4 6 (d2sp3) Re3 (CH2 Si Me3 ) 12
+6 6 (d2sp3) Re Me6
24
(v) MnCl2 +2 MgCl (CH5CMe3) ROR
[Mn (CH2CMe3)2]2 + 2MgCl2
or 4 MgRx
TMEDA +2Lime
[Re2 Me8]
(vii) ReCl4 +(THF)2+MgCl(CH2 SiMe3)
N
Re2( -CSiMe3)2(CH2SiMe3)4
2
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Table 1.8 : Representative Hydrocarbyls of Group 6, 7 and 8 Metals
Metal Oxidation Coordination Alkyl (or Aryl)
State Number
Fe +2 2 (sp) Fe (Mes)2 Mesitylene.
+2 4 (sp3) Fe {CH (CH3) (CN)} (CO)2 5C5H5),
Fe Ph (Co)2 ( 1C5H5),
FeR(Co)2 ( 1 C5H5)
Fe Me2 (dmpe)2
Co +1 5 (dsp3) Co (CF2 CF2H) (CO) 4
+2 4 (sp3) Co Ph2 (dipy);
[C0Me4]2-
+3 3 (sp2) [Co Ph2 ( 6C6H4 Me)]
+3 6 (d2sp3) CO (C=CR)63-
+4 4 (sp3) CO R4
6 (d2sp3) [C0(CH2Ph) (CN) 5]2-
Ni +2 2 (sp) Ni Bu2; Ni (Mes)2
+2 4 (sp3) Ni (CH2 Si Me3)2 (bipy)
Ni Et2 (biby);
Ni Me42-; Ni Ph42-
Ni Ph2 (dipy)
+3 3 (sp2) Ni Ph2 ( 6-C6H4Me)
6 (d2sp3) [Ni (CH2 Ph) (CN) 5]2-
Ru +2 6 (d2sp3) Ru(CH3) (I) (CO)2 (PPh3) 2
Rh +3 3 (sp2) Rh (Mes)3
6 (d2sp3) [Rh (Et) (NH3) 5 ]2+
Pd +2 4 (sp3) [Pd (>CH2 S Ph) 2] 4
Ir +3 6 (d2sp3) Ir Me (CI)(I)(CO)(PPh3)2
26
Ir Cl2 (C6H4Me)(CO)(PPh3)2
Pt +2 4 (dsp2) Pt Me2 (PPh3)2
Pt Me (O2C CF3)(PPh3)2;
trans Pt Cl (Ph)(PPh3)2;
Pt (C CR)Cl(PPh3)2
27
(3) Reaction of Anionic metal Complexe with organic Halides
(i) Na [Fe (CO)2 ( 5-C5H5)+ C6 F6 [Fe (Ph) (CO)2 ( 5–C5H5) +Na F
(ii) Na3 [CO (CN)5] + Ph CH2 Br Na2 [Co (CH2 Ph) (CN)5] + Na Br
(iii) Na [Co(CO)4+CH2=CH2 Br Co (CH2-CH=CH2) (CO)4 + NaBr
Co (CO)3 ( 3-C3H5)+CO
(4) Insertion Reactions
(i) Insertion of Multiple Bonded molecule in M-H Bond
FeH (CO)2 (n5 C5H5) + CH2 = CHCN Fe {CH (CH3) CN} (CO)2
( 5 – C5H5)
Co H (CO)4 + C2 Fe4 Co (CF2 CF2 H) (CO)4
[RhH (NH3)5]2++ C2H4 [Rh (C2H5) (NH3)5]2+
(ii) Insertion of Unsaturated molecules in Metal-Metal Bond
Co2 (CO)8 + C2F4 (CO)4 Co-CF2CF2-Co (CO)4
(iii) Insertion of Unsaturated Molecule in MC Bond
Trans Pt Cl (CH3) (PEt3)2 + CO Trans Pt (C:O) Ph (CO)4 (PPh3)
(5) Elimination Reactions
(i) Elimination of CO from Acyl Compound
Li [Co(CO)4] + F3C COCl Co (CO CF3) (CO)4 + LiCl
CO (CF3)CO)4+CO
(ii) Elimination CO2 from Carboxylates
Ni (CO2Ph)2 (biby) Heat
Ni Ph2 (biby) + CO2
28
[Pt (SO2Ph) Cl (PR3)2 Heat
PtCl (Ph) (PR3) + SO2]
IrCl2 (SO2C6H4Me) (CO) (PR3)2 Heat
29
(iii) [Pd(PPh3)( 5-C5H5)( 2-C2H4)+
R
[Rh(Bu) Cl (R)( 5- C5H5)]
(iv) Cis [Pt Cl2 (Py) ( 2-C2H4)] + Py Cis [Pt Cl2 (CH2CH2Py) (Py)]
1.3.37 Hydrocarbyls of Group 11 (d9 – metals)
d9- metals of group-11 in their + 1 to +3 oxidation states give
hydrocarbyls with coordination numbers 1 to 3. Maximum number of
these alkyls (or aryls) have tendency to polymerise (Generally tetramer
formation). The general method of their synthesis is halide exchange
reaction (Table 1.9) However some hydrocarbyls of silver are prepared
by ylide synthesis :
Table 1.9 : Representative Hydrocarbyls of Group-11
Metal Oxidation Coordination Alkyl (or Aryls)
State Number
(Hybridisation)
Cu +1 1 [Cu (C6F5)]4
[Cu (CH2 Si Me3)]4
[Cu R]4 (R=Ph, Me2 C6H3)
+1 2 (sp) Cu (Me5)2; Cu (C CR)2,
Cu Me2-; Cu (CH2CH2 PMe3)-2
+2 2 (sp) Cu R2 (R=CH2CH2PMe3)
+2 3 (sp2) Cu (Mes)-
Ag -1 1 [Ag Mes)]5,
+1 2 (sp) [Ag {C (SiMe3)3}2],
Ag (C CR)2-
Au +1 1 [Au (Mes]5; Au (C CR)
+1 2 (sp) Au Me2; Au (C CR)2
+2 2 (sp) Au (CH (Si Me)2 ] (L)
2
+3 3(sp ) [Au Ph3]
+3 4 3 (sp3 [Au Me4]
30
(1) Halide Exchange :
31
CHECK YOUR PROGRESS – 1
Notes : (1) Write your answers in the space given below.
(2) Compare your answers with those given at the end of this
unit.
(a) (i) Metal hydrocarbyls, the bonded organometallics are
........... and ................... derivatives of metals e.g. Me 3 Pt Cl,
IUPAC name of which is ...................................
(ii) On the basis of types of ligands metal – hydrocarbyls are
classified into (1) ........................ (eg ........................ and
....................., general formula .............................................)
and (2) ....................................... (e.g....................................,
general formula .........................................)
(iii) The hapticity of ligand is related with the .........................
..................................................................................................
..................................................................................................
(b) (i) Transition metal hydrocarbyls have been considered
................................................... compared to their main
group analogues. Hence, their synthesis has been ...............
...................., while ............................... is mainly due to
............................ rather than thermodynamic factor.
(iii) The most important path of their decomposition is
.............................................................................................
(c) (i) An example of halide exchange reaction is (Equation only):
.............................................................................................
(ii) An example of transmetallation is (Equation only) :
.............................................................................................
(iii) An example of ylide synthesis is (Equation only) :
..............................................................................................
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1.3.4: Stability of Transition Metal Hydrocarbyls
Compared to main group hydrocarbyls the transition metal analogues
are generally much less stable, although the instability is mainly due to kinetic
rather than thermodynamic factors. In view of much greater diversity in their
nature, it is rather difficult to attempt a simple generalization of their properties,
but an attempt would be made to correlate some of these on the basis of their
coordinative unsaturation and steric congestion.
The M-C bond in transition metal hydrocarbyls is also as strong as it is in
case of main group metal hydrocarbyls. We know alkyl and aryl groups are one
electron, monohapto-ligands. Alkyl and aryl radicals resemble with hydrogen
and halogens in the presence of unpaired electron. Thus, just like H. or .X they
also combine with metal atom sharing their unpaired electron, to form metal
alkyl or metal aryl.
H, CH3,.C6H5 , .X (X = F, Cl, Br, I)
M.+ .H MH Or M-H (Metal Hydride)
M. + .X MX Or M-X (Metal Halide)
M.+ CH3 MCH3 Or M-CH3 (Metal Alkyl)
M. + C6H5 MC6H5 Or M-C6H5 (Metal Aryl)
The nature of the bond, on the basis of electronegativity of metal may
vary from purely ionic to purely covalent. In ionic alkyls and aryls of Mn, Zn
and Eu hydrocarbon radical is an anion (i.e. in the form of rarbanion ion), which
is formed as a result of transfer of electron from valency shell of strongly
electropositive metal to valency shel of carbon (making the unpaired electron
present in alkyl or aryl radical paired) :
33
Covalent or polar – covalent alkyl or aryl may be supposed to form as a
result of overlapping of metal orbital having unpaired electron with the valency
orbital of alkyl or aryl radical having unpaired electron :
For example, where as (CH3 Co(CO)5 is stable upto – 20ºC only, CF3 Co
(CO)5, 91ºC, 91ºC, distills without decomposition. Fluorine makes M-C bond
more polar by attracting electrons towards itself. Thus the bond energy has an
34
increased ionic contribution. Further on increase of positive charge on metal
atom, contracts d-orbitals, which decreasing the non bonding interaction,
increases better overlap between bonding metal d-orbitals and ligand orbitals.
35
Another mode by which these derivatives tend to satisfy their
coordination environment is by forming polynuclear species through alkyl or
other bridging legands or through multiple metal-metal bonding. The
association through bridging would obviously be hindered by more ramified
ligands. thus resulting in mononuclear species. Formally these would be
coordinatively unsaturated yet they attain thermal stability probably due to
steric congestion of the ligands which inhibits approach of reactive species.
Thus one of the attractive areas of research since 1970s has been to prepare a
variety of sterically demanding ligands in an attempt to prepare transition metal
hydrocarbyls in low coordination states, e.g., [Ti{CH(SiMe3)2}3],
[Cr{CH(SiMe3)2}3], Mn{C (SiMe3}2], etc.
For any particular metal, the coordinative unsaturation will increase with
lowering of the oxidation state of the metal and lead to greater associative
tendency. For example, compared to the monomeric character of Ti (C 6H5)4, the
polymeric nature of {Ti (C6H5)2]n can be cited.
Transition metal hydrocarbyls may be of three types, i.e., neutral,
anionic, and cationic. The formation and stability of anionic species of the types
[Ti(C6H5)5] and [Zr(C6H5)6]2- can be understood as in these, the central metal
atoms are coordinatively less unsaturated than in the corresponding neutral
species. Ti(C6H5)4 and Zr (C6H5)4, respectively.
On the same grounds, one would not expect the cationic species to be
formed easily; in fact, these often require a chelating hydrocarbyl of the type
Me3 P=CH2 which for example confers stability on cationic species of the
types:
36
Generally, with the increase in atomic weight of a metal, the M-C bond
energy of transition metal hydrocarbyls gradually increases (Table 1.1) i.e. for
the same metal, 'E' values follow the order Ph > Me > Et. The interesting
observation of the higher value of 'E' for M-C (CH2SiMe3) compared to that for
M-C(CH2CMe3) bond could probably be ascribed to the greater steric effect of
the latter (neopentyl) group, which could possibly lead to lengthening of the M-
C bond.
37
called hydride transfer accompanied with alkene-elimination. This type of
reaction involves the transfer of a hydrogen from the second or carbon atom
of the alkyl chain to the metal, increasing its coordination number. The
resulting intermediate hydrido-alkene complex tends to lose alkene with the
formation of metal hydride which in some cases may decompose to metal and
hydrogen.
hydrocarbyls and the main examples involve metal methyls. The binary
permethyls such as TaMe5, WMe6, and ReMe6 are not very stable and tend to
decompose explosively with the formation of methane, e.g.,
WMe6 3CH4 + "W (CH2)3'
In view of the metal being in its highest oxidation state, an internal
oxidative addition of the type :
H
M CH 3 M CH 2
38
is not feasible for the above decompositions which could occur either via
homolytic fission (free radical mechanism) or elimination through a four-
centre transition state :
39
It has also been shown by crystallographic analysis that when a methyl
group is attached to a dº metal centre which has a less than 18-electron
environment, the one of the C-H bond of the methyl group is distorted in such a
manner that it lies within the bonding distance of the metal:
Such strong interactions between metal and a C-H group have been
shown to play a key role in cyclometallation and alkene polymerization
reactions.
(ii) Intermolecular reductive elimination pathway is the reverse of
oxidative addition reactions and can be represented as :
X
LnM LnM + X - Y
Y
Both the oxidation state as well as the coordination number of the central
metal 'M' are reduced by two units and hence, this type of pathway would be
confined to metals with stable oxidation states differing by two units, which is
more common with later transition metals.
40
A few examples of this type of pathway are given below :
(a) AuMe(PPh3) AuMe (PPh3) + C2H6
(b) Organometal hybrides often decompose by this route and such reactions
assume special significance in catalytic hydrogenation processes :
PtH(R)(PPh3)2 Pt (PPh3)2 + RH
(c) Reductive elimination frequently follows oxidative addition, and in many
important catalytic processes both these phenomena play a crucial role
An illustrative example of stoichiometric reaction is depicted below :
Au (CH2SiMe3) (PPh3) + MeI AuIMe (CH2SiMe3)(PPh3)
41
1.3.6 Characteristic Reactions :
Bonded transition metal organometallics exhibit great diversity in
their reactivity patterns, which obviously depend upon the nature of the
metal as well as on the other ligands present. The chemical reactions of
importance to our discussion fall into six main categories : (a) metal-
carbon bond cleavage reactions, (b) elimination of an alkene and proton
abstraction, (c) replacement of one hydrocarbyl ligand by another. (d)
adduct formation, (e) redistribution reaction. and (f) insertion reactions
into metal-carbon bond.
2HCl HCl
(iv) Cis[PtCl2(PEt3)2] CisPt Me2 (PEt3)2 Cis [Pt+Cl (Me)(PEt)2]
2 CH4 CH 4
42
(b) Elimination of alkene with proton transfer ( Decomposition)
(M = Ti Or Zr)
(iv) [Mn (CH2 Si Me3)2]a+2 Li CH2 Si Me3 Li2 [Mn (CH2 Si Me3)4]
(f) Insertion Reactions : Unsaturated ligands CO, CO2, CNS, SO2 etc. show
insertion in to M-C bond to give new products:
43
(i) CO insertion :
O
Cu Me (Et2O) (PPh3)2 CO
2
78º C
(iii) Although NC, CO are isoelectronic but its insertion is not extensively
studied :
R
C
Ti R (OEt2) ( 5-C5H5)2 + Ph – N C ( 5-C5H5)2 Cu
N
Ph
44
1.4 Organo Copper in Organic Synthesis
45
(iii) In, , - unsaturated carbonyl systems, it selectively attaches with -
Carbon atom,
(iv) It has special ability to replace various types of halogen atoms by methyl
group,
(v) It reacts with allytic acetate by SN-1 reaction.
(vi) Reacts with epoxides to form open ring alkylated alcohols, and
(vii) It adds to acetylene-esters
The specific reactions of LiCu Me2 with reference to organic synthesis,
are :
1. Halogen Substitution
(i) trans PhCH = CH Br + Li Cu me2 trans PhCH = CH Me
(ii) C6H5I + Li Cu me2 C6 H5 Me
(iii) C5H11 Br + Li [Cu But2] But (CH2)4 CH3
2. Conjugated Additions
O O
(i) Me CH = CH C Me + Li Cu Me2 Me2 CH CH2 C Me
46
3. Alkylation of Allyl Acetate
Me2 C – CH CH CH2 But + Li Cu Me2 ButCH = CH CH2 But
OOCMe
4. Alkylation of Epoxides
OH
OH
5. Formation Ketone from Acid- Chloride
O O
(i) N C(CH2)10 C Cl + Li Cu Me2 N C(CH2)10 C Me
(ii) But C Cl + Li Cu Pr42 But C prt
47
Check Your Progress – 2
Notes : (1) Write your answers in the space given below.
(2) Compare your answers with those given at the end of this
unit.
(a) (i) The unstability of transition metal hydrocarbyls is due to
................................ of the metal atom.
(ii) On the basis of ......................................... of the metal atom,
the nature of metal hydrocarbyl varies from ..........................
to ...................................
(iii) Abscence of ......................... or/and presence of .....................
atom increases the stability of metal hydrocarbyls.
(iv) The hydrocarbyl formed in the lower oxidation state of the
metal have very high tendency ................................................
(b) (i) Metal hydrocarbyls decompose by three processes
(x) -------------------------------------------------------------------------
(y) -------------------------------------------------------------------------
(z) -------------------------------------------------------------------------
(ii) During elimination, alkyl compound decomposes with
transfer of ........................ ion, along with elimination of an
..........................; while decomposition, due to ..................
mechanism, proceeds with ............................... mechanism in
which the intermediate product is ...........................................
(iii) The example of elimination is (Equation only)
.............................................................................................
(c) The synthetic applications of organocopper are due its following
characteristics :
(i) Strong ..................and very high .......... positions, as
compared to carbonyl group.
48
.............................................................................................
(ii) ................................ towards groups like ............................ or
................................ present in acid – chlorides.
(iii) In , unsaturated systems it selectively attaches .................
(iv) Reaction with allylic acetate is ............................................
(v) Reacts with epoxides to form .............................................
.............................................................................................
After going through this unit you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far :
Organometallic compounds are organic compounds of metals. In these
compounds metal – carbon bond is present. Because organic compounds
are hydro carbons or their derivatives, hence in organo-metallic
compounds, generally those compounds are included in which one or
more hydrocarbon radicals are directly linked with metal atom.
Compounds of metals with alkyl radicals are called metal alkyls, while
those with aryl radicals are known metal-aryls (i.e. hydrocarbyls).
Almost all metals of periodic table form hydrocarbyls. For a long time it
was considered that transition metal hydrocarbyls are unstable compared
to their main group analogues. However the unstability is not
thermodynamic but is of kinetic nature.
Metal alkyl and aryls are named according to IUPAC nomenclature, thus
Zn (C2H5)2 is diethyl Zinc (II), and Me3 Pt Cl is chlorotrimethyl Platinum
(IV).
49
On the basis of nature, bonding and structure organotransition metal
compounds are classified in to following three groups:
(a) Ionic,
(b) bonded covalent and
(c) bonded covalent Compounds
50
2. Use of radicals like t butyl or isopropyl having crowded -
hydrogen atoms,
3. In place of - carbon, use of radicals with Si, Ge and Sn atoms,
and
4. Use of stabilizing agents.
For preparation of hydrocarbyls of transition metals of different groups of
periodic table, the following methods are generally used: (1) Halide
exchange, (2) Ylide synthesis (3) Transmetallation, (4) Insertion of metal
hydride alkene, (5) Action of anionic metal complexes with organic
halides, and (6) Elimination reactions.
Alkyl and aryl radicals resemble with hydrogen and halogens in the
presence of unpaired electron. Thus they are mono hapto ligands similar
to hydrogen and halogen and combine with metal atom to form metal
alkyl and metal aryls.
During synthesis of transition metal hydrocarbyls, with the increase in
electroneutrality tendency, increase in M L , back bonding ( M L , -
bonding) is seen. This stabilises the compound.
Similarly, coordination-unsaturation in transition metal hydrocarbyls
results in tendency for polymerisation.
Alkyls (or Aryls) of transition metal, due to coordination- unsaturation,
are kinetically unstable. They decompose using one of the three
pathways:
(i) transfer of substituent from bonded hydrocarbyl radical to
metal atom,
(ii) Intermolecular elimination, and
(iii) homohytic fission of M-C bond.
51
In elimination, one substituent, R, from bonded alkyl radical is
transfer to metal atom, along with the elimination of a carbene molecule.
This phenomenon is less seen in transition metal alkyls.
In elimination, alkyl molecule decomposes with the transfer of
hydride ion along with elimination of an alkene molecule.
The important reactions of these compounds are classified in to six
groups :
(i) Decomposition of metal-carbon bond :
TiMe4 + 4 Me COOH Ti (O2 C Me)4 + 4 CH4
ROR
CP R Cp R
Zr + CO Zr
CP R Cp C R
O
52
dimethyl cuprate, which has many important characteristics which prove
it a better synthetic reagent :
(i) In , unsaturated carbonyl systems, it selectively attaches with
carbon atom
53
(c) (i) MCl4 + 4 LiMe MMe4 + 4 LiCl
(ii) 2 TiCl4 + ZnMe2 2TiCl3Me + ZnCl2
(iii) ZrCl4 + n Me3P = CH2 Zr Cl4 (CH2 PMe3)n
2. (a) (i) Coordinate unsaturation
(ii) Electronegativity
Purely ionic to purely covalent
(iii) Hydrogen
F, Cl or O
(iv) Polymerisation.
(b) (i) (x) Transfer of substituent from bonded hydrocarbyl
radical to metal atom (y) Intermolecular reductive
ilimination (z) Homolytic fission of M-C bond..
(ii) Hydride (H-) ion
Alkene molecule
Homolytic fission
free radical mechanism
four centred.
(iii) Pt Cl (CH2CH3) (PEt3)2 Pt HCl (PEt3)2 + C2H4
(c) (i) Strong nucleophilicity
alkene and halide
very high affinity
(ii) cyano or ester
nertness
(iii) Carbon atom
54
UNIT-2 COMPOUNDS OF TRANSITION METAL-CARBON
MULTIPLE BONDS
STRUCTURE
2.1 Introduction
2.2 Objectives
2.6.3 Reactions
55
2.1 INTRODUCTION
56
as carbyne (or alkylidyne) complexes (the systematic (IUPAC) nomenclature of
these two classes of compounds uses the suffix-ylidene or – ylidyne
respectively.
2.2 OBJECTIVES
57
(ii) Homonuclear carbene derivatives: These are compounds with the
metals in high oxidation states and further in these, the carbene which is
bound to hydrogen and carbon atoms only is nucleophilic in nature.
Discovered by R.R. Shrock in 1974, these can be more appropriately
termed as alkylidene complexes in view of the homonuclear nature of the
ligands involved. After the discoverer, these are also called Shrock
Carbenes.
1. Fischer Carbene
With the use of alkylating agents like R3O+, BF4- or MeOSO2F etc. in
place of diazomethane (CH2N2), now synthesis of these compounds has become
quite easy. By now a large number of compounds have been synthesised. In
these compounds metal is in low oxidation state and on carbene cabon -
accepting auxillary ligand and substituents are linked. In its reactions carbene
carbon behaves as an electrophilie. In these Fischer – carbenes, structure of
carbene carbon may be represented as follows:
58
2. Shrock Carbene
H
Ta(CH2CMe3)3 Cl2 + 2LiCH2 CMe3 CMe4 + (Me3C CH2)3 Ta=C
+2 LiCl
CMe3
59
The nucleophilic property of Shrock carbene may be represented by:
TiC H
TaCl Me 55 (C H ) TaMe
5 5 2
2 3 2
Ph C
3
60
2 (C H ) TaMe
Ph PcH
3
(C H ) TaMe (CH )
5 5 2 2 5 5 2 2
13
In the C n.m.r. spectroscopy the alkylidene carbon resonance is
invariably found at low field (200-300 ppm downfield of SiMe4). Such a large
chemical shift appears to be characteristic of many types of carbon atoms which
are multiply bonded to some extent extent to a transition metal. Another
distinguishing feature of alkylidene complexes is low 1Jchα coupling constant
values (75-100 Hz) found for example, in neopentylidene and benzylidene
complexes having less than 18 valence electrons (e.g. TaCl(CH2CMe3)
(CHCMe3)(η5-C5Me5) = 14e, IJchα = 76 Hz).
61
Further 'H n.m.r signals for hydrogen atoms(s) attached to alkylidene
carbon fall in the range δ – 2 to 12. (The values are lowest for 18-electron
complexes), while the infrared studies provide another interesting feature; the
C-Hα stretching frequency is surprisingly low (2400-2600 Cm-1) in the electron
deficient (< 18e) complexes. (A low value for Vchα correlates well with a low
value for 'Jchα.) Based on these physicochemical data. The alkylidene complexes
are defined as compounds in which an sp2 dybridized carbon donor atom also
has a vacant p-orbital which which permits a back – bonding interaction with
filled orbitals on the metal. (Fig 2.1.)
Fig. 2.2.
62
2.4.3 Reactions
Alkylidene complexes (M=CRR') are chemically very labile and the
carbon atom bound to the metal exhibits a strong nucleophilic character,
whereas metal centre is electrophilic. The chemical and spectroscopic studies
show that M=C bond, due to low electronegativity of metal atom (placed at left
side in d-block series), is polarised such that the carbon atom attached to metal
develops negative charge. Corresponding molecular orbital explainations show
that pz orbital of CR2 group is of lower energy compared to dx orbital of metal
atom. As a result, π electron density concentrates on carbon atom. Thus, this
shows strong nucleophitic propery, while the metal atom remains electrophilic.
Fig. 2.3.
The reactions of these compounds are divided in to three groups.
63
low temp.
(Me3CCH2)3 Ta(:CHCMe3)+HCl TaCl(CH2CMe3)4
(iii) With Lewis acids such as Al2Me6 also, these form addition complexes,
e.g.:
Cp 2Ti ( CH 2 ) Me Me3 SiBr [Cp 2Ti(CH 2 Si Me3 ) Me] Br
(iii) Interactions with organic halides have been shown to proceed via SN2
mechanism, e.g.:
Mel
TaMe(:CH2)(5-C5H5)2 TalMe((5-C5H4) ((5-C5H5)2
64
(iii) Reaction with Ester
(c) Decomposition reactions. The alkylidene complexes are more labile even
at room temperature, that they undergo decomposition reactions.
65
2.4.4 Applications in Organic Synthesis
The reactions given in section 2.4.3 indicate clearly that alkylidene
complexes may be utilise in organic synthesis. The most important reactions in
this respect are:
(2) Compare your answers with those given at the end of this unit.
(a)(i) Compounds with metal-carbon double bond are known as .............
complexes, while those with metal-carbon triple bond are called
............... complexes. IUPAC names of these compounds are .................
and .................. organometallics respectively.
66
(ii) The general formula of fischer carbene is .................... and that of shrock
carbene is .................... where R = R' = ................ .
The above reaction procedure has been extended by using AI 2C6, GCl3,
or, AI2Br6, or PBr2 PH3 instead of BX3, e.g.,
67
pentane
W{C(OMe)Ph}(CO)5 + Al2Br6 - 300C
WBr(CPh) (CO)4+ CO
+ Al2Br5(OMe)
- 500C
W{C(OLi)Ph}(CO)4 + PBr2Ph3 WBr(CPh) (CO)4+ CO
+ LiBr + P(O)Ph3
2. Fission of M M Bond :
Interactions of compounds of the type (RO)3 WW(OR)3 with
acetylenes, R'CCR', unexpectedly yield carbne complexes via cleavage of
acetylenes :
5
C5 H 5 Cl2 Ta C
(i) PMe3
Ph (ii ) Ph3 P CH 2
( 5 C5 H 5 ) ( PMe3 )CITa CPh
or
68
5. From Metal Alkoxides :
69
formation of a triple bond with metal. Out of these, bond is towards the metal
atom, while two π-bonds are metal dπ –ligand pπ-bonds. Structures of a few
typical complexes are illustrated in Fig. 2.4. and 2.5.
Fig. 2.4
Fig.2.5.
2.5.3. Reactions
There are two important reaction of alkylidyne complexes, which are
used in organic synthesis as catalyst :
1. Synthesis of new alkynes (Exchange Reaction) :
CMe
2. Insertion Reaction
W (C CMe3 )(dme) Cl 3 Me C C Me Cl 3 W Me
Me
70
2.5.4. Application in Organic Synthesis
The reactions given in section 2.5.3. are important with reference to
application in organic synthesis.
2.6. FISCHER CARBENE
A large number of such Fischer type complexes are now known for a5
d8 metals (usually in 0 or + 1 formal oxidation states, assuming the carbene to
be a neutral two electron ligand).
These Fischer type complexes are 18 electron species with the metal in
formally 0 or + 1 oxidation state, these are also characterized by having at least
one stabilizing resonance form and in showing reactivety at C-carbene with
necleophiles.
3. Alkenes.
71
(i) From coordinated Carbonyls :
OLi
W (CO) 6 LiR (OC) 5 W C R
72
2. From Metal – Carbene Compounds :
( X OMe, NH 2 , NMe2 )
Or ( P.Ph3 ) 2 Cl3 Rh{: C( N Me2 ) H }2PEt 3 ( PEt 3 ) 2 Cl3 RH {C( NMe2 ) H } 2PPh3
73
substituted carbenes, and involves interaction of various metal derivatives with
highly electron rich alkenes such as the bis(imidazolidizidene) mono, bis,
neutral, and cationic carbene derivatives involving a majority of the transition
metals have been prepared by this procedure :
74
shortened in view of the -bonding involved.
The carbene group : C(OMe)Ph is a monohapto ligand which provides an
electron pair to the metal tungsten for a -bond formation. The alkylidene
ligand may have (Fig.2.6.) either of the conformations singlet (a) or triplet (b).
The vacant px and py orbitals in the two conformations respectively could be
expected to form -bonds with px and dxz orbitals of the metal (W) in the latter
case. Actually the dxz and dyz orbitals in the complex are of similar energy and
comprise a composite orbital of cylindrical symmetry, making it possible for
the -interaction between the alkylidene and the metal to occur in all planes
intermediate between the dxz and dyz planes. The conformation adopted by the
complex would therefore not depend on maximizing the -bonding, but would
be controlled by the non-bonding interations between the alkylidene ligand and
the nearby carbonyl groups; the conformation would consequently be staggered
to minimize there latter interactions.
Thus, above bonding description reveals that the singlet carbene which
has a filled orbital of -pseudosymmetry and an empty p-obital of -pseudo-
symmentry enter into synergic bonding interactions with transition metals
forming LM -bond and ML -bond, similar to that in case of alkene. (Fig.
2.7.).
75
Structures of some carbene complexes are given in Fig. 2.8., a perusal of
which indicates Cr-C distance 2.0A0 and CC distance 1.5 A0, while CO
and CN distances (1.3A0 and 1.8A0 respectively) are also smaller, similar
to MC bond distance. These confirm metal-carbon multiple bond.
Fig. 2.7.
2.6.3. Reactions
76
1. Displacement of ligands coordinated with metal :
OMe
(i) (CO) 5 Cr C (OMe) R PR3 (CO) 4 ( PR3 )Cr C
R
Substituti on
(ii) (CO) 5 Cr C (OMe) R Py (CO) 5 Cr Py CH 2 CH (OMe)
and fission
N = CPh2
(ii) (CO)5 Cr = C (OMe)R + HN = CPh2 (CO)5 Cr = C R
Nucleophilic Ph
(iii) (CO) 5 Cr C (OMe)Ph Li Ph (CO) 5 Cr C
Addition Ph
77
5. Insertion on double bond
(i)
OMe OMe
(ii) (CO) 5 Cr C Ca(CN ) (CO) 5 Cr N C CH
Ph Ph
i.
1300
ii. Heat
CH2=CHOR
i.
500C
78
ii.
(i)
(ii)
79
(iv) Synthesis of special compound containing alkyle, carbene and
carbyne ligands (Churchill and Youngs, 1979):
80
reagents like CO and MeOH:
In reaction (I), the carbide formed from hexa coordinated carbide has
butterfly structure.
2. Compare your answers with those given at the end of the unit.
81
........................................................................................................
(ii) In alkylidyne complexes the two π bonds are from metal
.............................. to ....................... bonds and the bond angle is
approximately .......................
(b)(i) Fischer Carbenes are given by ................ metals in their lower oxidation
states .............. and ..................
(ii) The singlet carbene the σ orbital of pseudo symmetry is ........ and the π
orbital of pseudo symmetry is ............, links with metal atom, analogous
to alkene, forming ..................... and ................. bond.
(x) .................,
After going through this unit, you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far:
Compounds in which divalent carbon is bound to a transition metal
(with M-C double bond) are known as carbene complexes. Like wise
compounds in which a transition metal is attached by triple bond with
carbon is called carbyne complex. In IUPAC nomenclature carbene
compounds are known as alkylidene compounds, while carbyne
compounds are called alkylidyne compounds.
82
Carbene compounds are named after the names of their discoverers as
fischer carbenes and shrock carbenes.
83
These reactions are used in organic synthesis.
Alkylldyne ligands, CH or CR, are monohapto three electron ligands,
which combine with a metal atom forming a triple bond.
Free carbene is found in both signlet and triplet states. In signlet state
sp2 hybridisation is used. Electron pair is present in a sp2- hybrid
orbital while in triplet state, sp-hybridisation is utilised. One electron
each is present in the two unhybridised p-orbitals.
84
(iv) Insertion on the double bond.
These compounds are used in the synthesis of alkene, ether and esters.
In carbido complex four metal atoms are linked with carbon atom. An
important carbido complex is carbido-iron, C(Fe)4 which has a
butterfly structure.
(ii) Nucleophilic
SN-2
2.(a) (i) Substitution of methoxy group from carbene complex by halide
ion.
(ii) d π, orbital
Ligand p π
180o
85
(b) (i) d5 – d8
0
1
(ii) Filled
empty
L→M, σ – bond
M→L, π – bond
(c) (i) (x) Alkene (y) Ether and (z) Ester
(ii) C (Fe)4
86
UNIT-3 TRANSITION METAL -COMPLEXES-I
Structure :
3.1. Introduction
3.2. Objectives
87
3.1. INTRODUCTION
88
(ii) Allylic organometallics ; three electron donors, e.g., Ni ( 3 C3 H 5 ) 2
3.2. OBJECTIVES
89
3.3. ALKENE COMPLEXES
Only the latter transition metals (especially in their lower oxdation states)
are known to form to form complexes with monoalkenes. Alkene complexes of
transition metals are generally heteroleptic in nature, e.g., Re(CO) 4 (alkene)+,
MoX(CO)2(alkene)3, and Fe(CO)2 (alkene) (5C5H5), although a few
homoleptic derivatives also are known, e.g., Co(2C2H4)n (where n = 1 or 2);
Ni(2C2H4)n, Ni(2C2H4)n and Pd(2C2H4)4 (where n = 1 or 3) have been
isolated in a low-temperature matrix using metal-vapour synthetic procedures.
90
K 2 Pt Cl4 CH 2 CH 2 K Pt Cl3 2 C2 H 4 KCl
M CO6 NC 2 C C CN 2 M (CO) 5 2 C2 (CN ) 4 CO
M Cr , Mo or W
Temp.
MX (CO) 3 ( C5 H 5 ) H 2 C CH 2
5
M (CO) 3 ( 2 C 2 H 4 ) ( 5 C5 H 5 )
Pr es
M=Mo or W
Mn (CO) 3 X H 2 C CH 2 140
Mn(CO) 3 ( 2 C2 H 4 ) X
Atoms
Mn (CO) 3 ( 5 C5 H 5 ) H 2 C CH 2
UV
Mn(CO) 2 ( 2 C2 H 4 ) ( 5 C5 H 5 ) CO
H CH 3
||
5
C5 H 5 CO Fe.CH 2 C CH 3 5 C5 H 5 CO 2 Fe CH 2 C
Base (Pr otonation ) OH
H CH
5
C5 H 5 CO 3 Mo CH 2 CH CH 2 5
C5 H 5 CO 3 Mo CH 2 C
OH 3
In these reactions organic cations, Ph3C+, R3O etc, have been found quite
useful.
91
(c) Reductive Alkenation
EtOH
RhCl3+C2H4 [{Rh Cl( 2-C2H4)}2]
92
(a) -Bonding
(b) -Bonding
93
involved in the formation of metal-olefin complexes results in weakening
of the olefin double bond, which is demonstrated in a lowering in the
v(C=C) stretching by 50-160 Cm-1, For example, the v(C=C) stretching
frequency, observed for free propene at 1652 Cm-1 is lowered by 148 Cm-
1
on complex formation (e.g. in K[PtCl3(2- C3H6)]) to 1504 Cm-1.
The strength of -back bonding of the metal with the alkene depends on
the nature of the other ligands bonded to the metal. The observation that
in complexes of the type, RhL(C2H4)(C2F4) (where L= acac or C5H5), Rh-
C(C2F4) bond distances (2.01-2.02A) are shorter than the analogous Rh-
C(C2H4) bond distances (2.17-2.19A), substantiates the expectation that
the electron withdrawing substituents would enhance the -acceptor
ability (C2F4>C2H4) of a particular alkene.
Firstly, one has to pick out the valency atomic orbitals of the atoms in the
molecule under consideration. For example, in a transition metal alkene
complex such as Zeise's salt. [PtCl3(H2C-CH2)], the metal valence atomic
orbitals are 5d, 6s and 5p. The ligands may have and valence orbitals;
for example, in an alkene the valence orbitals are composed of sp2 hybrid
orbitals and the -valence orbitals are 3pz. These two pz orbitals (one on
each carbon atom), in ethene, on in-phase linear combination, give a
molecular orbital that covers the entire molecule. In the first
approximation the energy or electrons in this -orbital has a value
considerably lower than that of any of the other -electrons. The next
94
higher energy molecular orbital is formed by substraction (i.e. out-of-
phase linear combination) of the two pz atomic orbitals.
95
However, as the temperature is raised, the rotation of ethene molecule
about the metal-alkene bond tends to make all the ethene protons
magnetically equivalent and the sparate lines collapse into a broad signal.
The C-C bond distance (1.37A) in the complex (Fig. 3.1) is slightly
longer than in the free ethene (1.34A) which can be explained to arise
from the population of electrons in the orbital of ethene, which brings
about a change in the nature of the hybrid orbitals at carbon atoms. For
example, a perusal of Fig. 3.4 shows that the C-C bond length and (NC)
C (CN) angle in coordinated tetracyanoethylene are increased
considerably with a concomitant change in the sp2 hybridization in the
parent alkene to sp3 type in the complex.
96
Fig. 3.4
Hence these complexes are generally represented as in Fig. 3.5 (a) and
(b) or the resonance hybrid of the two structures.
Fig. 3.5
A considerable amount of X-ray structural data, which has become
available in more recent years, supports the following general conclusions:
97
The structures of these complexes are analogous to distorted square,
which generally polymeries e.g. the bis-ethylene complex of rhodium chloride
is a dimer:
After linking with metal, the chemistry of the ligand changes to a great
extent. Free alkene is fond of electrophilic reaction, rather than a nucleophilic
reaction. But after coordinated with metal, ethylene becomes nucleophilic,
perhaps the carbons become more positive.
3.3.3 Reactions
Chemical properties of alkene complexes depend on the following facts:
(a) For metal atoms alkenes are weak ligands hence can be replaced
by strong ligands like cyanide, t-phosphine etc.
(b) After coordination with metal, electron-density in -bonding
orbital decreases, but increases in antibonding * orbital, As a
result alkene molecule is activated and takes part in different types
of reaction. These reactions are important for industries.
(c) 2- alkene complexes give many products using nucleophilic
reactions.
98
the nucleophile attacks at an alkenic carbon of the alkene. These general types
of reactions are summarized in schemes I to V:
99
Scheme-V
100
typical examples involving metal – alkene intermediates in the homogeneous
catalyzed organic synthesis are illustrated as follows:
(a) Hytdrogenation:
(b) Hydrosilylation:
(c) Carboxylation:
(d) Hydroformylation:
(e) Oligomerisation:
101
(f) Isomerisation:
(g) Dismutation:
3.4 ALKYNE
Although alkyne complexes have been studied less extensively, yet their
chemistry reflects some rather fascinating features. For example, in alkynes the
presence of two -bonds at right angles to each other provides greater
possibility for bonding of alkynes with metals. Of the two -bonds available in
alkynes, either only one or both may be donated to a metal.
The reactions of alkynes with different transition metal species can occur
in different ways. In the simplest cases, alkynes replace only one two – electron
donor ligand from the original complex. In these, only one of the two -electron
pairs of alkynes takes part in the reaction.
102
is linked in place of ethylene molecule, e.g. L2Pt (RCCR) or (Pt(RCCR)X3)-.
The structure of these complexes are analogous to that of alkene complexes. In
these complexes one of the dsp2 hybrid – orbitals of the metal links with a pair
of electrons from bond of RCCR. Alkynes are more electronegative
compare to alkenes, hence they are comparatively stronger -acceptor.
Alkynes have two bonding and two * antibonding orbitals, which are
quite capable of interacting metal orbitals. Out of these one or two electron
pairs may be donated to metal atom. It is assumed that these are utilized in a
mononuclear complex eg. in Mo (Meso. tetra-p-tollyl porphyrin) (HCCH).
In this complex two electron pairs are donated to cobalt atom and
HCCH molecule forms a bridge between two cobalt atoms.
103
(b) Mn (CO) 3 ( 5 C5 H 5 ) RC CR Mo ( RC CR) ( 5 C5 H 5 ) 2 CO
(c) MC (CO3 ) ( 5 C5 H5 )2 Ph C C Ph UV
(iii) The two pairs of -Electrons Donated in two Metal Atoms with the
Alkyne Functioning as a Bridging Ligand:
The reaction of iron carbonyl with acetylene, RCCR often give special
104
products (Fig.3.6.)
Fig. 3.6
3.4.2 Bonding and structure
Alkynes with two -bonds may bind metals utilizing one or both sets of
-electron pairs, thus providing greater possibilities for bonding by alkynes.
105
In the formation of a -bond of the above type, the CC bond should be
expected to become weaker; this is reflected in the lowering of the vCC
absorption by about 150 Cm-1 in the metal acetylide compared to that in the free
acetylenes.
106
Fig. 3.8 Structure of (a) Pt(PPh3)2(2-PhCCPh).
(b) (5-C5H5)Ni(-PhCCPh)Ni(5-C5H5)
3.4.3 Reactions
As expected, the reactivity of coordinated alkynes would be to some
extent influenced by the nature of the metal involved. Thus alkyne complexes
of transition metals in low oxidation states generally undergo reactions with
electrophiles, while complexes of transition metals in higher oxidation states as
well as cationic complexes are usually reactive towards nucleophilic moieties.
A few examples of these types of behaviour are illustrated below:
107
(a) Displacement reactions
The displacement of one alkyne by another has been exploited for the
preparation of new alkyne complexes:
Pt ( PR3 ) 2 ( HC CH ) RC CH Pt ( PR3 ) 2 ( RC CH ) HC CH
CO
RC CH [ RC C Pd 11]
Pd ( II )
RC CCO2 R
R' OH
Ni (CO) 4
HC CH H 2 O H 2 C CHCO2 H
150 0 C , 130 atm
PdCl 2 / thiourea
HC CH CO MeOH MeO2 CCH CHCO2 Me
O2
108
(b) Reactions with Nucleophiles:
HCl
(i) Pt(PPh3)2 (2 Ph C C Ph) Pt(PPh3) Cl2 + Ph' CH = CH Ph
109
CHECK YOUR PROGRESS – 1
(2) Check your answers with those given at the end of the unit.
110
3.5 3- ALLYL COMPLEXES
In view of the above, one has to be very careful while suggesting the
structures for allylic derivatives. The 18–electron rule is useful in distinguishing
between 3 – and 1-allyl types, but the third type can be identified only by X-
ray structure determination. The , 2 – allyl derivatives are fluxional (cf. unit
8) with the metal changing positions from one side to another of the plane
comprising the three allylic carbon atoms:
111
Just as alkene complexes show similarity to carbonyls, the delocalized
allylic system CH2-CH-CH2 acting as a formal three – electron donor can be
linked to NO ligands in metal nitrosyl derivatives. These allylic derivatives
have also been visualized as a sort of halfsandwich, i.e., intermediate between
alkene and the sandwich compounds.
Other transition metals like Ti, Zr, Hf, Th, V, Nb, Ta, Cr, Mo, W, Fe, Co
and Pt also follow this reaction. In some cases (e.g. Ni(II) and Pd (II)) this
reaction takes place in equimolar ratio and the product is M(3-allyl)x.
112
3. Protonation of complexes (e.g. tetrahapto 1-3 Butadiene):
113
114
Z
Fig. 3.9
Structure (I)
In Mn(CO)4 CH2 CH = CH2 (Structure II) it is trihapto ligand :
Structure (II)
115
In, trihapto complexes, e.g. Bis(3-allyl) nickel (structure III), the
terminal two carbon atoms of allyl group are at distance of 202.9 pm from the
metal atom and the central carbon atom is at the distance 198.0 pm. The C-C-C-
bond angle is 120.50 and the average C-C distance is 141.6 pm. Hence the
terminal carbon atoms are sufficiently bent, resulting in good -overlapping.
The C-C distance is in accordance with -conjugated system. Anti (trans from
meso) are bent away from metal and syn (cis from meso) are bent towards
metal atom.
Structure IV
116
Other example include Mo and Cr complexes (Structure V and VI) :
Structure V
117
1600cm-1, The conversion of a 1-bonded allyl group into a -arrangement is
of greater interest from a mechanistic view point and has been more generally
studied in detail by n.m.r. technique. An example of such a rearrangement
which has been followed by i.r. and Hn.m.r. spectroscopy is illustrated below:
(Fig. 3.10.)
The important reactions of 3-allyl complexes are (a) Insertion, (b) Metal
exchange, (c) Halide exchange, (d) Displacement and (e) Nucleopuilic reactions
:
(a) Insertion reaction :
Cl
2[ Pt ( PPh3 ) 2 ( C 3 H 5 )] Cl 2CO ( Ph3 P) 2 Pt
3 CHCl3
COCH CH CH 3 (Cis and trans)
118
(b) Metal exchange reaction :
(i) on metal :
119
CHECK YOUR PROGRESS -2
(2) Compare your answers with those given at the end of the unit.
(a) (i) The ................... structure of allyl group show that it is .................
electron donor, i.e. ........................ ligand or ................ electron
donor ...................... ligand in its behaviour.
After going through this unit, you must have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far :
120
Only the later transition metals, especially in their lower oxidation states
are known to form complexes and govern EAN-rule.
Alkene ligands are dihapto two electron donor. Its filled -orbital,
donates electron pair to vacant orbital of metal to form LM -bond;
and the filled metal orbital donates electron pair to antibonding * orbital
to form ML -bond.
121
The homogeneous catalysed reactions are of industrial importance, these
include : (i) hydrogen, (ii) hydrosilylation, (iii) attack on carbon atom of
alkene.
In alkynes, two -bonds are perpendicular to each other, hence they can
not work as bidentate ligands. However in binuclear complex it can link
with two metals forming a bridge.
122
reactions, (ii) reaction with nucleophilic reagents and (iii) electrophilic
reactions. These reactions are used in organic synthesis.
This can behave both as a monohapto and trihapto forms. Most general
form is trihapto. In it carbon-carbon distances are equal, which indicate
mobility of electrons in three -orbitals.
In trihapto complex, the terminal two carbon atoms of allyl group are at a
distance of 202.9 pm from metal atom and the central atom is at a
distance of 198.0 pm and the C-C-C- bond angle is 120.50 and the
average distance is 141-6 pm. As a result terminal carbon atoms are bent
considerably, resulting in effective -overlapping.
123
Displacement and (v) Nucleophilic reactions.
These reactions are of great importance in organic synthesis.
(iii) dsp2
Vacant
Filled
Bonding-
Vacant antibonding *
filled –d-
(ii) alkene
Dewar Chatt Duncanson scheme
(iii) -donor
-acceptor both
(iv) Cis
trans
2(a) (i) Resonance
One
Monohapto
124
three
trihapto
(ii) alkene
sandwich
1
2
Py an dyz
(ii) Carbon
sufficiently bent
-overlapping
125
M.SC. (FINAL) CHEMISTRY
BLOCK-II
126
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
Block-II : Synthesis
This block includes three units, unit 4, 5 and 6.
127
UNIT – 4 TRANSITION METAL - COMPLEXES – II
Structures
4.1 Introduction
4.2 Objectives
4.3 4 Complexes
128
4.1 INTRODUCTION
4.2 OBJECTIVES
The main aim of this unit is to discuss nature and bonding of transition
metal complexes of 4 to 6 hepto ligands. After going through this unit you
should be able to:
129
discuss the nature of bonding in these complexes,
4.3 4 COMPLEXES
Benzene
(C6H5)2 + Co2 (CO)8
Heat
Benzene
C2F4 + Co2 (CO)8
Heat
130
4.4 BUTADIENE COMPLEXES
2. nkc
(i) Fe (CO) CH CH CH CH Fe(CO) ( 3 C H ) 2CO
5 2 2 3 4 6
3. (ii) Fe (CO) CH CH CH CH
UV
Fe(CO) ( 4 C H ) 4CO
5 2 2 4 62
4.
131
(vii) RhCl CH CH CH CH RhCl (η 4 C H ) 4CO
3 2 2 4 6 2
(ii) M 3 CH CH CH CH M ( 4 C H )
2 2 4 6
(M = Mo, W)
In the above structure the ligand is in the cis configuration, the plane of
four carbon atoms being nearly parallel to that of the carbonyl groups. The
metal atom is equidistant from each of the four carbon atoms in the diene and
the carbon – carbon bond lengths are all equal.
132
with the metal-based orbitals of suitable symmetry for donation and acceptance
of electron density.
133
Orbitals are important, then the geometry of butadiene moiety is pretty
well like.
Structure - IV
Structure-V
4.4.3 Reactions
1. Substitution Reactions:
In these reactions diene ligand is nucleophilically substituted.
Fe (4-C4H6) (CO)3 + 2PPh3 Fe (CO)3 (PPh3)2 + C4H6
134
2. Nucleophilic addition:
In these reactions due to nucleophilic reaction of H-, R-, CN-, MeO-, R3N
etc. (Nucleophilies) on carbon of oleffins, diene ligand or any other
ligand is displaced or addition on carbon taken place:
3. Electrophilic addition
In these reactions there is addition of proton or eliminatation of proton:
135
5. CYCLOBUTADIENE COMPLEXES
Structure - VI
136
4.5.1 Methods of Preparation
Many other cyclobutadiene complexes are now known, among them the
unsubstituted - cyclobutadiene iron tricarbonyl prepared by the
Structure VII
137
S.5.2 Bonding and structure
138
(a) (b)
139
Fig. 4.3 : Butadiene – Metal - Bonding
4.5.3 Reactions
Cyclobutadiene appears to be too labile for independent existence, thus,
when released from their captive traps (combinations with transition metals),
these highly reactive molecules rapidly decompose, dimerize or isomerize or
react with suitable organic substrates to generate new novel organic products:
140
Other reactions are decomposition and dimerisation, or isomerisation
giving novel products:
141
Dewar Benzene
Structure IX
142
Or
Structure X
Structure XI
Cyclo Octatetraene Cyclopentadinyl Cobalt (II)
Structure XII
Cyclo Octatetraene Tetracarbonyl Molybdenum
143
CHECK YOUR PROGRESS – 1
2. Compare your answers with those given at the end of the unit.
(x) ...............................................................
(y) ...............................................................
2. In Ru3 (Cy Oct.)2 (CO)4 structure, the apex Ru atom receives ................
electrons from ........................ molecules, while each of the base Ru atom
receives ......................... electrons from ..................... molecule.
144
4.7 CYCLOPENTADIENYL, 5 – COMPLEXES
Metallocenes:
145
All metals of the first transition series from titanium to nickel inclusive
are now known to form neutral bis- (-cyclopentadienyl) complexes, and those
of vanadium, chromium cobalt and nickel are isomorphous with ferrocene. Bis
(-cyclopentadienyl) derivatives of zirconium, technetium, ruthenium, osmium,
rhodium and iridium have been prepared, those of ruthenium and osmium have
been shown to have a structure similar to that of ferrocene, but with the rings in
the eclipsed conformation. They are less stable than ferrocene. The order of
their reactivity being:
CP2Fe < Cp2 Ni < CP2 Co < Cp2 V < Cp2 Cr < Cp2 Ti
Methods of Preparation:
Fe3 CpMgBr
Fe 2 Fe (η5C H )
2CpMgBr
5 5 2
Ferrocene forms orange crystals which sublime at 100º and are insoluble
in water but soluble in many organic solvents. It undergoes many of the
conventional electrophilic substitution reactions of organic chemistry, notably
acylation, alkylation, halogenation and metallation; but it is more resistant than
benzene to hydrogenation.
146
Alternatively, the action of cyclopentadiene on a metal halide in a basic solvent
may be used; for example,
The complexes of other metals (Cr, Fe, Co, Ni) are also prepared using
similar method. However, now a days in place of sodium cyclopentadinide,
thallium cyclopentadinide is preferred. Because sodium is a strong
electropositive, hence the product is reduced to give hydride complex. The use
of thallium salt considerably reduces this possibility.
THF
5
Re Cl2 Na C5 H ReH ( -C5H5)2
5
(Re flex )
MCl2+2C5H6+2NH(C2H5)2(5-C2H5)2 MNH2+Cl;(M=Fe,Co,Ni)
2C5H6+Fe (atom)Fe(5-C2H5)2 + H2
Fe (CO)5+C10 H12 Fe(5-C2H5)2 + (CO)3
147
A, almost exactly the same as in benzene. The inter – ring distances is 3.22 A,
and the iron-carbon distance 2.04 A. The compound is diamagnetic.
X-ray studies of solid ferroene indicate its sandwich structure. The two
cyclpentadienyl group are placed in this structure in staggered configuration.
However electron diffraction studies in vapour state show them in eclipsed
form.
Fig. 4.5
148
Thus skeleton is obtained. Each sp2- hybrid has single electron. In
addition, each pz orbital of each carbon atom has one electron, which is used
for formation of mobile (delocalized) -bond. In this way five electrons from
five carbon atoms and an additional electron (obtained due to Cp - formation)
give total six electrons, which are placed in three of the five -bonding orbitals
(as electron pair); while remaining two -bonding molecular orbitals remain
vacant. During combination with central Fe (II) [d2 sp3- hybridised], each Cp
coordinates giving three electron pairs (Fig. 4.6).
Now the filled orbitals (t2g) of Fe (II), form back - bond with vacant
antibonding orbitals (* MoOs) of CP-. In this way each Cp- links as donor
and - acceptor, with Fe (II). Thus sandwich complex is formed (Fig. 4.7).
Eclipsed Fe Fe Staggered
149
150
Fig. 4.7 Ligand group orbitals and matching atomic orbitals
of iron for ferrocene.
151
On molecular orbitals theory, five p orbitals (one on each carbon atom)
are available for orbital formation, linear combinations of which can give rise to
three bonding and two antibonding molecular orbitals. The most strongly
bonding overlap (i.e. all the wave functions on one side of the ring have the
same sign) and this is designated as 'A'. At slightly higher energy there is a
doubly degenerate set of molecular orbitals (E1) each of which has one nodal
plane. This is followed by another doubly degenerate set of molecular orbitals
with two nodal planes and yet higher energy. A schematic representation of the
- molecular orbitals of cyclopentadienide anion is given in Fig. 4.8 with their
energy increasing from bottom to top.
To construct the ten ligand group orbitals of ferrocene from two
cyclopentadienide anion, the five group molecular orbitals of one
cyclopentadienide anion are combined in pairs with a similar set from the
second C5H5 in symmetric and antisymmetric and matching atomic orbitals of
iron for ferrocene are shown in Fig. 4.8(a). In an LCAO molecular orbital
treatment of bonding in metallocenes, of the atomic
Fig. 4.8 The molecular orbitals formed from the set of five porbitals of
the cyclopentadienide anion C5H5
152
153
Fig. 4.8 (b)
154
orbitals of the metal ion are grouped by symmetry. Thus for ferrocene, the
metal orbitals are designated as: d, dz2 (a1), pz (a2u); dxz, dxz dyz (e1g); px, py (e1u);
dxy, dx2–y2 (e2g) where 'a' and 'e' indicate nondegenerate and degenerate where g
and u represent symmetric and antisymmetric nature of the orbitals.
If both rings have the positive lobes of their lowest energy orbitals on the
sides nearer to the metal, then s and dx2, orbitals would have the correct
symmetry; if one of the rings has the positive lobe nearer to the metal and for
the other ring, the negative lobe is nearer to the metal, the pz orbitals has the
correct symmetry.
Provided that the energies of the two component sets are not too far apart,
each of the combinations shows in Fig. 4.8 (b) represents a bonding MO of the
molecule. Although for simplicity, these are not shown, yet there are an equal
number of antibonding combinations. It is quite apparent that no metal orbitals
of appropriate symmetry are available to combine with the degenerate ligand
sets labelled as e2u.
The simplified molecular orbital energy – level diagram that results from
the above considerations for ferrocene is shown in Fig. 4.9
155
(Ligand orbitals) (Metallocene orbitals) (Metal orbitals)
156
higher energy filled set of e1g and e1u symmetry; and even a higher energy
unfilled set of e2g and e2u symmetry. It can be noticed that the metal dxz and dyz
orbitals have been found to interact more effectively with the cyclopentadienyl
ligand group orbitals than the metal s (a1g); px, py (e1u); and pz (a2u) orbitals.
These bonds are believed to provide most of the stabilization that holds the
ferrocene molecule together. The antibonding e2g ligand orbitals interact with
the metal 3dx2-y2 and 3dxy orbitals producing slightly bonding molecular
orbitals which comprise mostly of metal orbitals. Based on the above simple
molecular orbitals picture, it is not surprising that the ferrocene in which all the
nine molecular orbitals of the lowest energy are occupied by electrons, is the
most stable metallocene.
If in ferrocene only all the bonding and non bonding orbitals are filled
(i.e. nonbonding orbitals are not filled) then nine electron pairs (total 18
electrons) will be necessary. This confirms 18 electron – rule. (But this is not
universal see table 4.1)
Table 4.1.
Compound Colour Unpaired Electronic
Electrons Configuration
Cp2V Pink 3 e22g a11g
Cp2Cr Red 2 e23g a11g
Cp2Mn Amber 5 e22g a11g e12g
Cp2Fe Orange 0 e24g a12g
Cp2Co Pink 1 e24g a12g e11g
Cp2Ni Green 2 e24g a12g e12g
157
(Reference: Ferrocene):
v (CH) v (C=C) (CH) π (CH) Unsymmetrical M–R
Bent Stretching
3086 1408 1001 854 490 478
2909 1104 814
(ii) (Cp)2 MLx, "bent metallocene" derivatives, in which the plane of two
cyclopentadienyl rings are at an angle and L represents some other ligand
such as hydride, alkyl(aryl), halide, alkene, carbon monoxide or even 1
– cyclopentadienyl groups and 'x' may have values generally from one to
three (Fig. 4.10).
Important examples are Cp2 ReH, Cp2 Ti Cl2 and Cp2 Ta H3.
Fig. 4.10
(iii) (Cp)3 M2, Triple deckers, e.g. Cp3 Ni2. In this complex there is layered
158
structure involving cyclo-pentadienyl rings and nickel atoms (Fig. 4.11)
Fig. 4.11
An important fact, about these compounds is that the elements with even
number of atomic number form dimer, while the elements with odd number of
atomic number (V, Mn and Co) form monomer. This behaviour is quite
opposite to that of normal carbonyls. All these compounds follow EAN rule.
(Fig. 4.12):
159
Fig. 4.12 Cyclopentadinyl Carbonyl Complex
Fig. 4.13
160
Theoretically metallocene should give aromatic reactions. But these are
generally not stable in these reactions. As compared to benzene, metallocene
are more reactive with electrophilic reagents.
1. Aromatic Properties
161
2. Protonation of metal
(i) Fe (5-C5H5)2 H+ [FeH(5-C5H5)]
5. Reduction Reaction
Metal atom or / and cyclopentadienyl group is reduced
(i) Co+ (5-C5H5)2 + Na BH4 Co (5C5H5) (4-C4H6)
C2H2NH2
(ii) Fe (5-C5H5)2 + Li Fe + 2 C5H5-
5. Addition reaction
162
4.8 ARENE ORGANOMETALLIC COMPLEXES
The simplest and the most common six electron donor arene ligand is, of
course, benzene, but other arene moieties can also function in the same fashion.
Although the first 6-arene metal complexes were reported by Hein as early as
1919, yet it took almost 35 years for their definitive characterization by the
synthesis of the prototypical "sandwich" compound Cr (6 – C6H6)2 by E.O.
Fischer in 1955. Since then the chemistry of arene metal complexes has
undergone remarkable transformations leading to the synthesis of 6 – arene
complexes of almost all transition metals (d2 – d8)
163
benzene on chromium (III) chloride in the presence of aluminium and
aluminium chloride, the resulting cation [(-C6H6)2 Cr]+ being reduced to the
neutral complex by dithionite or allowed to disporportionate in the presence of
aqueous alkali:
3Crl3 AlCl 3 6C6 H 6 2 Al 3 Cr ( 6 C6 H 6 ) 2 AlCl
4
Cr ( 6C6 H 6 ) 2
Na2 S2O4 50 C
0
164
(iii) Metal vapour synthesis. This technique has provided a synthetic route for
a very wide range of bis (arene) metal - complexes, many of which
were inacessible by conventional techniques:
(i ) cocondenses,77 K
MnCl 2 arene M ( 6 arene) 2
(ii ) warm
165
Cr
Fig. 4.14
166
Fig. 4.15 Molecular Orbital diagram of dibenzene chromium.
167
Characteristic Properties
These compounds resemble metallocenes in their solubility in organic
solvents and in volatility, but these are generally more reactive than their 5 –
C5H5 analogues and are thermally and aerially less stable. For example, Cr (6-
C6H6)2 undergoes facile oxidation to [Cr (6-C6H6)2]+. This ease of oxidation of
Cr (6-C6H6)2 is also reflected by its reaction with alkyl halides, generating
alkyl radicals which undergo usual disproportionate / addition reactions:
1000 C
Mo( 6 C6 H 6 )3 6 PF3 Mo ( PF3 ) 6 2C6 H 6
600 Air
( 6 C6 H 6 ) 2 Re H ( 6 C6 H 6 ) Cr ( 6 C6 H 7 )
168
lkbDyksgsDlsu
( 6 C6 H 6 ) 2 Cr Li Bu ( 6 C6 H 6 Li) Cr ( 6 C6 H 6 Li)
700 C
Due to metallation with lithium, the product can be used for many
organic synthesis:
3. Redistribution:
Cr ( 6 C6 H 6 ) 2 Cr (CO) 6 Cr (CO)3 ( 6 C6 H 6 )
4. Redox reaction:1
2 Cr ( 6 C6 H 6 )2 O2 2H 2O 2[Cr ( 6 C6 H 6 )2 ] OH
Na2 S 2 O4
CR
C C C
O O O
Fig. 4.16
169
Check Your Progress – 2
2. Compare your answers with those given at the end of the unit.
(b) 1. The first 6- arene complex was ........................................... which was
synthesised by ................................. in..................................
170
4.9 LET US SUM UP
After going through this unit, you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far:
In butadiene complex, the ligand is in cis – form and the layer of four
atoms, is parallel to three carbonyl groups. The metal atom is at
equidistance with the four atoms.
171
Cyclooctatetraene is not aromatic analogous to cyclobutadiene. The
important 4-complexes with the ligand are Ru, Co and Mo – complexes.
In which it donates four electron to the metal atom.
In Ru3 (Cy O.T.)2 (CO)4 molecule, the apex Ru atom receives 8 electrons
from two cyclo – octa tetraene molecules (of 4 electrons from each
molecule), while out the two base Ru atoms, each one gets four electrons
from one cyclooctatetraene molecule during the combination.
The order of their reactivity is: CP2 Fe < Cp2Ni < Cp2 Ni <Cp2 Co <
Cp2V < Cp2Cr < Cp2Ti
X-ray diffraction studies show that the ligands are in a staggered form in
the sandwich structure. While electron diffraction studies show them to
be in eclipsed configuration.
172
Metallocenes should generally give aromatic reactions. But these
molecules do not remain stable in these reactions.
(iii) 4px
Molecular orbitals
Same symmetry
173
b. (i) Ru, Co and Mo
Metal
Four electrons (2 pairs of electrons)
(ii) Eight
Cyclo Octatetraene
Four
Cyclo-Octatetraene
2.(a) (i) Twocyclopentadinyl rings
Fe (5-C5H5)2
(ii) Pentagonalantiprismatic
X-ray diffraction
Cyclopentadinyl groups
(iii) Antibonding
Bonding
Non bonding
Nine
18 electron rule
(iv) Cp3 Ni2
Fischer
1955
(ii) px
C5H 5
174
three
three
antibonding molecular orbitals
(iii) Octahedral
d2 sp3
________________________
175
UNIT-5 TRANSITION METAL COMPOUNDS WITH BONDS TO
HYDROGEN
STRUCTURE
5.1 Introduction
5.2 Objectives
176
5.1 INTRODUCTION
177
5.2 OBJECTIVES
178
5.3.1 Hydrides of Transition Metals
Titanium, zirconium and hafnium all react with hydrogen at a convenient
rate in the temperature range 300-400º.At such temperatures the hydride phase
has a considerable equilibrium dissociation pressure and the amount of
hydrogen taken up increases with the hydrogen pressure applied to the system;
compositions with hydrogen in excess of TiH1.9 may be obtained, but they are
more often in the range TiH 1.5-1.8. Similar considerations apply to all hydrides
made directly from the elements.
179
compositions in the range CrH0.5-1 and has a hexagonal structure while the
other, which is much less stable, has a cubic structure with the upper limit of the
hydrogen content corresponding with the formula CrH1.7. This phase appears to
be similar in structure to the dihydrides referred to above.
Palladium metal has long been known to absorb hydrogen readily, even
at room temperature Limiting compositions in the range PdH0.6-0.8 are observed.
The metal lattice of the hydride phase is face-centred cubic, as in the metal
itself, but the lattice parameter is increased by roughly 3 per cent. Neutron
diffraction studies have shown that the hydrogen atoms occupy the octahedral
holes in the metal structure and are randomly distributed. Copper hydride,
which differs greatly in its mode of preparation, properties and structure from
these metallic hydrides. Copper is the only transition metal, to form a well-
characterized hydride. Hydrogen has a low solubility in metallic copper and no
hydride, been known since 1844, when Wurtz prepared it by the reaction shown
below:
180
occurs above about 50º. Decomposition by aqueous hydrochloric acid gives
CuCl and H2, and hydrogen is also evolved rapidly in alkaline solution. The
hydride is a reducing agent in aqueous media, converting, for example, chlorate
to chloride.
Formerly these hydrides were classed with carbides, nitrides and borides
as interstitial compounds, and it was thought that hydrogen atoms, like other
small atoms, could be accommodated in interstices in the metal lattice
producing distortion but no change in type. In fact, the metal atoms in most of
these hydrides occupy a sub-lattice which is different from that of the parent
metal, and the interstitial compound concept also fails to describe the bonding
and changes in the physical properties of the metal which occur if it is hydrided.
181
electrons from the metal to hydrogen, also leads to the conclusion that there will
be a falling away in metallic properties as the hydrogen to metal ratio increases.
182
aqueous solution, in which slow hydrolytic decomposition occurs. Hydrogen is
evolved quantitatively on treating the salts with an aqueous acid, and the metal
is deposited.
The structure of K2ReH9 has been established by X-ray analysis and
neutron diffraction. The latter is particularly important as it enables the
positions of the hydrogen atoms to be determined. The crystal is hexagonal with
three molecules per unit cell. In the anion (Fig 5.1) six of the hydrogen atoms
are at the corners of a trigonal prism with the metal atom inside it, and there is
one hydrogen atom outside the centre of each of the prism faces in an equatorial
position.
The Re-H bonds are all approximately of the same length (1.68 A). The
proton n.m.r. spectrum shows a single high.field peak at 18.4 p.p.m. for the
rhenium compound and at 19.1 p.p.m. for the technetium compound, the latter
99
being broadened because of unresolved coupling with the Tc nucleus. All of
the hydrogen atoms thus appear to be equivalent on an n.m.r. time-scale, and all
undergo slow deuterium exchange in alkaline D2O. The infrared spectrum
shows the bending and stretching modes which are characteristics of the M-H
bonds.
183
Each hydrogen bonded to the metal atom may be regarded as a ligand
with a charge of -1 (i.e. as contributing two electrons to the metal atom). If the
latter is taken as being in the +7 state with sixty-eight electrons, addition of
eighteen electrons from the nine ligands gives an effective atomic number of
86, equal to that of radon. The nine electron pairs fully occupy all of the
available orbitals of the metal atom (5d56s6p3) and all of the nine hydrogen
orbitals.
The two compounds appear at the moment to be unique among transition
metal derivatives, though rhodium forms two compounds, Li 4RhH4 and
Li4RhH5, which may be similar. The former is made by heating rhodium
powder with LiAIH4 at 600º and reacts on further heating with hydrogen to give
the latter.
184
CHECK YOUR PROGRESS – 1
Notes : (1) Write Your answers in the space given bellows
(2) Compare your answers with those given at the end of this
unit.
(a) (i) The dihydride of titanium has FCC ...................... structure
with hydrogen atoms in ........................... holes, of which
there are two per metal atom. This structure changes to
........................... structure below 310K.
(ii) Wurtz prepared copper hydride with emperical formula
............... This hydride is a ........... agent in aqueous solution.
(iii) There are two current theories of bonding in metallic
hydrides :
(a) .....................................(b) .............................................
(b) (i) Re and Tc both form hydride complexes containing
................ ion.
(ii) In this anion ................... of the hydrogen atoms are at the
corner of ...................... prism, with metal atom inside.
(iii) Each hydrogen atom bonded to ...................... atom may be
regarded as a ligand with a ...........................
185
been isolated and they now constitute an important facet of carbonyl chemistry.
Other ligands, notably tertiary arsines and phosphines, the cyclopentadienyl
radical and the cyanide ion, have, however, also been found to stabilize the M-
H bond in transition metal complexes. The chief interest in these compounds
centres on the metal-hydrogen bond, and they are therefore considered here as
hydrides. Only in compounds, K2 ReH9 and its technetium analogue, is
hydrogen with certainty to be bonded to a transition metal in the absence of
other ligands.
186
anions. Iron pentacarbonyl, for example, gives a solution which is colourless i
the absence of air and which on treatment with dilute mineral acid evolves iron
carbonyl hydride (H2Fe(CO)4) as an evil-smelling gas which can be condensed
to a white solid melting at -70º. It decomposes rapidly above-10º, giving
hydrogen and products of decomposition of the Fe(CO)4 radical. A number of
other carbonyl hydrides, among them HMn(CO)5, HRe(CO)5, H2Ru(CO)4,
H2Os(CO)4 and HCo(CO)4, can be obtained by acidification of solutions
containing carbonylate anions obtained, Other methods of preparation include:
NaBH4
Fe(CO 4 )I 2
H 2 Fe(CO) 4
THF
200º
Mn 2 (CO ) 10 H 2
2HMn (CO ) 5
200atm
150º
1
Co 4CO H 2 HCo(CO) 4
2
50atm
187
The acidities of mononuclear carbonyl hydrides vary very widely:
HCo(CO)4, though only slightly soluble in water, is as strong as a mineral acid
in methanol; for H2Fe(CO)4 pK1 and pK2 are 4.5 and 1.4 respectively; and for
HMn (CO)5 pK is 7. It seems clear that the hydrogen atoms in all these
compounds are bonded to the metal, though only for HMn(CO)5 is the structure
known in detail: the molecule is octahedral, with the Mn-H distance equal to
1.60A. Two physical properties may be used to show that metal-hydrogen
stertching vibration, which occurs at 2200-1700 Cm-1, is lowered by the
theoretical factor of 2 on deuteration, and transition metal hydrides have
Many di-or polynuclear carbonyl hydrides have been reported, but their
formulae are not always related to those of known carbonylate anions, and
many of the structures assigned to them rest only on spectroscopic evidence.
We may, however, mention HRe2Mn(CO)14 (Fig 5.2) and the anion [HCr2
(CO)10]- (Fig. 5.3) In each case spectroscopic and diffraction data are consistent
with a linear symmetrical hydrogen bridge and eclipsed carbonyl groups on the
metal atoms bonded to hydrogen. The structure of [HFe3(CO)11]- is closely
related to that of Fe3 (CO)12 and can be regarded as the latter with one bridging
carbonyl replaced by hydrogen. In [HFe2(CO8]- a hydride ion similarly replaces
a bridging carbonyl group in the Fe2(CO)9 structure. Among several carbonyl
hydrides obtained by dissolution of metal carbonyls in alkali to give
unidentified coloured products, and subsequent acidification, are H3Mn3 (CO)12
188
(from Mn2 (CO)10), and H4Os4(CO)12 and H2Os4(CO)13 (from Os3(CO)12).
Evidently considerable molecular rearrangements can take place in what might
seem to be a simple process.
H2 molecule can link (coordinate) with metal atom with out breaking
H-H bond. The first such complex was [W(CO)2 (H2) (P' Pr3)2 (Fig 5.4). Now a
large number of such complexes have been prepared, which may be regarded as
the link between H2 molecule and dihydrido complexes. Molecular Orbital
descriptions indicate that electron density from H-H bond is transferred to
vacant orbital of metal, along with formation of back bonding in * orbtal
of H2.
Figure 5.4
189
Similarly Brown and associates have confirmed linking of CH ----Fe in
[Fe(3.C8H13) {P(OMe)3}3]- complex using neutron diffraction method. While
Calvart and Shaple have on the basis of NMR studies of triosmium complex,
given proof of C.H-Os bond (Fig 5.5)
Figure 5.5
ethanol
190
IrCl3 (PEt2Ph)2 + OH- + C2H5 OH
-
IrHCl2(PEt2Ph)2 + CH3CHO + H2O + Cl
In this particular case all three chlorine atoms may be replaced by
hydrogen if excess of reagent is used. By using the deuterated alcohol
CH3CD2OH in the above reaction, it is found that the hydrogen introduced into
the metal complex is that bonded originally to the carbon in the alcohol.
Reaction is believed to involve replacement of chlorine by the ethoxide ion with
subsequent transfer of hydrogen from the ethyl group to the metal. The
intermediate step can thus be formulated as
Various phosphines and arsines have been employed, and a large number
of such derivatives of metals in Groups VII and VIII isolated.
191
IrH2 Cl(PEt3)3 dryHCl
IrHCl2 (PEt3)3
º at120atm 3 3
130
Vat 2
120atm
2 3 2
The reactions that are of interest are those of the M-H bond, such as its
conversion to an M-Cl bond by mild chlorinating agents (e.g. CHCl3), and the
loss of hydrogen on heating, with formation of a binuclear complex, Addition
of olefins across the M-H bond also occurs (e.g. C5H5 Fe(CO)2H with C2F4
192
gives C5H5 Fe (CO)2 CF2 CF2H(, while diazomethane converts C, H, Mo
(CO)3H to C5H5 Mo(CO)3 (CH3).
A number of hydrides are also known in which the cyclopentadienyl
radical and hydrogen are the sole ligands bonded to the transition metal. The
first to be prepared was [ReH( C5H5)2], made by the reaction
Re Cl 5 Na(C5 H 5 THF
Re H(C5 H 5 ) 2 NaBH 4
All are crystalline solids which sublime in high vacuum and are soluble
in organic solvents. They are unaffected by water or alkali but oxidize in the air.
Reaction with chloroform converts the M-H bond to M-Cl.
193
5.4.4 Cyanide Hydride
Hydrogen is absorbed by an aqueous solution of a cobalt salt to which
cyanide ion has been added to form [HCo(CN)5]3- and the proton n.m.r.
spectrum of the product shows a chemical shift of 17.5 p.p.m. relative to water.
This high value makes it certain that a Co-H bond is present in the complex.
Slow decomposition of the solution occurs in the absence of oxygen at room
temperature and it is very sensitive to atmospheric oxidation. The oxidation
product is the anion [Co(CN)5OOH]3-, the potassium salt of which has been
prepared by hydrolysis of K6 [(CN)5Co-O- OCo (CN)5], and which has a
characteristic electronic absorption spectrum. Solutions containing the cobalt
cyanide hydride can act as homogeneous catalysts in various hydrogenation
reactions (e.g. the conversion of styrene to ethylbenzene). Reaction also occurs
with tetrafluoroethylene to give the ion [Co(CN)5CF2CF2H]3-, which is again
strong support for the presence of the Co-H bond in the ion. A solid salt NaCs2
[Co(CN)5H] has recently been isolated.
194
CHECK YOUR PROGRESS – 2
195
5.5 LET US SUM UP
After going through this unit, you would have achieved the objectives
stated earlier. Let us recall what we have discussed :
The monohydrides VH and TaH both have body centred tetragonal metal
sublattice, in addition these have a body centred orthorhombic
modification.
Nickel and palladium hydrides (NiH .7), PdH 0.8) are formed by
196
absorbing hydrogen at low temperature.
A great impetus to the study of metallic hydrides has come from the
potential use of some in nuclear reactor technology. Zirconium hydride,
with the metal and hydrogen both having low thermal neutron capture
cross section is important in this respect..
Titanium and some of the other metals which form hydrides have high
neutron capture cross section and could find specialized applications as
shielding material.
Rhenium and technetium both form complexes containing the [MH 9]2- X-
ray and neutron diffraction studies show that the crystal of K 2ReH9 has
hexagonal structure with three molecules per unit cell. In the anion six of
197
the hydrogen atoms are at the corners of a trigonal prism with the metal
atom in side it, and there is one hydrogen atom outside the centre of each
of the prism faces in an equatorial position.
H2 molecule can link (coordinate) with metal atom without breaking H-H
bond. The first such complex was [W(CO)2 (H2) (PPBr3)2
198
Brown and associates indicated that there is CH-Fe link in [Fe (n3-
C8H13) {P(OMe)3}3}- complex, using neutron diffraction studies.
Calvart and Shaple have, on the basis of NMR studies of tri osmium
complex, given proof of C-H-Os bond. This type of coordination of C-H
bond has been called 'Agostic interaction' which is supposed to be three
centred two electron bond analogous to the bonds present in B-H-B and
WHW.
Transition metal hydrides with tert phosphine was trans [Pt HCl (PEt 3)2],
by reducing Cis [PtCl2 (PEt3)2] at 90º with dilute solution of hydrazine
hydrate.
Various phosphine and arsines have been employed and a large number
of such derivatives of metals in groups VII and VIII isolated.
199
The important compounds prepared in this series are ReH (5 C5H5)2,
MoH2 ( C5H5)3 WH2 ( C5H5)2 and TaH2 ( C5H5)2.
200
2(b) (a) (i) H2 Fe (CO)4
evil smelling gas
(ii) diffraction
hydrogen
eclipsed
hydrogen
(iii) H-H bond
Vacant
bonding
H2
201
UNIT-6 HOMOGENEOUS CATALYSIS-I
Structure:
6.1 Introduction
6.2 Objectives
202
6.1 INTRODUCTION
203
be represented in a cycle form with the continuous regeneration of the original
active catalyst. Such catalytic reactions have achieved greater importance in
industrial processes, but the role of transition metal organometallics as synthetic
(stoichiometric) reagents is also beginning to make an impact in
organometallic/organic synthesis.
6.2 OBJECTIVES
204
cyclopentadienyl and arenes with reference to their important synthetic
uses and
205
enhance product specificity by lowering the activation barrier for one path or by
raising it for another. Reactions at a catalytic centre or site are believed to
involve the intermediate formation of weak catalyst-reactant bonds which have
the effect of loosening the bonds in the reactants prior to reaction. Many
catalytic reactions taking place in homogeneous (both catalyst and reactants are
in one phase) solution have been interpreted in terms of the formation of an
activated (or intermediate) complex.
206
8. Reactions of coordinated cyclopentadienyls
9. Reaction of coordinated arenes.
(v) With Lewis acids such as Al2Me6 also, these form addition complexes,
e.g.:
207
Cp 2Ti ( CH 2 ) Me Me3 SiBr [Cp 2Ti(CH 2 Si Me3 ) Me] Br
(iii) Interactions with organic halides have been shown to proceed via SN2
mechanism, e.g.:
Mel
TaMe(:CH2)(5-C5H5)2 TalMe((5-C5H4) ((5-C5H5)2
208
(b) Reaction with Unsaturated Organic Compounds
In view of their proposed role in alkene metathesis reactions the
interactions of unsaturated compounds with alkylidene complexes assumes
special significance:
(c) Decomposition reactions. The alkylidene complexes are more labile even
at room temperature, that they undergo decomposition reactions.
209
Applications in Organic Synthesis
210
are:
1. Halogen Substitution
(ii) C6 H5 I + Li Cu Me2 C6 H5 Me
(iv)
(v)
2. Conjugated Additions
(i)
(ii)
(iii)
211
3. Alkylation of Allyl Acetate
4. Alkylation of Epoxides
(i)
(ii)
(i)
(ii)
W (C CMe3 )(dme) Cl 3 Me C C Me Cl 3 W Me
Me
212
6.4.3. Reactions of Coordinated Carbenes
As we know in carbene complexes, whre metal ion is nucleophilic,
carbene carbon is electrophilic. These complexes give various types of
reactions:
OMe
(i) (CO) 5 Cr C (OMe) R PR3 (CO) 4 ( PR3 )Cr C
R
Substituti on
(ii) (CO) 5 Cr C (OMe) R Py (CO) 5 Cr Py CH 2 CH (OMe)
and fission
N = CPh2
(ii) (CO)5 Cr = C (OMe)R + HN = CPh2 (CO)5 Cr = C R
Nucleophilic Ph
(iii) (CO) 5 Cr C (OMe)Ph Li Ph (CO) 5 Cr C
Addition Ph
213
5. Insertion on double bond
(i)
OMe OMe
(ii) (CO) 5 Cr C Ca(CN ) (CO) 5 Cr N C CH
Ph Ph
i.
1300
ii. Heat
214
2. New alkene from decomplexed carbene :
CH2=CHOR
i.
500C
ii.
(ii)
215
4. Synthesis of special compound containing alkyle, carbene and
carbyne ligands (Churchill and Youngs, 1979):
2. Compare your answers with those given at the end of the unit.
(x) ..........................................
216
(y) ..........................................
(z) ..........................................
(x) ..........................................
(y) ..........................................
217
reactions.
218
219
Scheme-V
(i) Hydrosilylation:
220
(j) Carboxylation:
(k) Hydroformylation:
(l) Oligomerisation:
(m) Isomerisation:
221
(n) Dismutation:
Pt ( PR3 ) 2 ( HC CH ) RC CH Pt ( PR3 ) 2 ( RC CH ) HC CH
222
alkyne complexes with reagents other than alkynes:
CO
RC CH [ RC C Pd ]
Pd ( II )
RC CCO2 R
11
R' OH
Ni (CO) 4
HC CH H 2 O H 2 C CHCO2 H
0
150 C , 130 atm
PdCl 2 / thiourea
HC CH CO MeOH MeO2 CCH CHCO2 Me
O2
223
(e) Reaction with Electrophilies:
HCl
(i) Pt(PPh3)2 (2 Ph C C Ph) Pt(PPh3) Cl2 + Ph' CH = CH Ph
The important reactions of 3-allyl complexes are (a) Insertion, (b) Metal
exchange, (c) Halide exchange, (d) Displacement and (e) Nucleopuilic
reactions:
(a) Insertion reaction :
Cl
2[ Pt ( PPh3 ) 2 ( C 3 H 5 )] Cl 2CO ( Ph3 P) 2 Pt
3 CHCl3
COCH CH CH 3 (Cis and trans)
224
(b) Metal exchange reaction :
(i) on metal :
225
(ii) On ferminal C-atom of allyl group :
a) Substitution Reactions:
In these reactions diene ligand is nucleophilically substituted.
Fe (4-C4H6) (CO)3 + 2PPh3 Fe (CO)3 (PPh3)2 + C4H6
b) Nucleophilic addition:
In these reactions due to nucleophilic reaction of H-, R-, CN-, MeO-, R3N
etc. (Nucleophilies) on carbon of oleffins, diene ligand or any other
ligand is displaced or addition on carbon taken place:
226
c) Electrophilic addition
227
Other reactions are decomposition and dimerisation, or isomerisation
giving novel products:
228
Dewar Benzene
229
2.
Protonation of metal
(iv) Fe (5-C5H5)2 H+ [FeH(5-C5H5)]
230
6. Reduction Reaction
Metal atom or / and cyclopentadienyl group is reduced
(iii) Co+ (5-C5H5)2 + Na BH4 Co (5C5H5) (4-C4H6)
C2H2NH2
(iv) Fe (5-C5H5)2 + Li Fe + 2 C5H5-
5. Addition reaction
231
6.4.10 Reactions of Coordinated Arenes
Unlike the cyclopentadienyl group, arene ligands are readily displaced
from complexes by other neutral ligands, such as carbon monoxide, phosphines,
2, 2' – bipyridyl, etc. Some important reactions are as follows:
1000 C
Mo( 6 C6 H 6 )3 6 PF3 Mo ( PF3 ) 6 2C6 H 6
600 Air
( 6 C6 H 6 ) 2 Re H ( 6 C6 H 6 ) Cr ( 6 C6 H 7 )
lkbDyksgsDlsu
( C6 H 6 ) 2 Cr Li Bu ( 6 C6 H 6 Li) Cr ( 6 C6 H 6 Li)
6
700 C
Due to metallation with lithium, the product can be used for many
organic synthesis:
8. Redistribution:
Cr ( 6 C6 H 6 ) 2 Cr (CO) 6 Cr (CO)3 ( 6 C6 H 6 )
9. Redox reaction:1
2 Cr ( 6 C6 H 6 )2 O2 2H 2O 2[Cr ( 6 C6 H 6 )2 ] OH
Na2 S 2 O4
232
10. Friedel – Craft Acylation
CH 3COCl
( C6 H 6 ) 2 M ( 6 C6 H 6 ) M ( 6 C6 H 5CH 3 )( M Cr , Mn)
6
CR
C C C
O O O
Fig. 4.16
Notes : (1) Write your answers in the open space given below.
(2) Compare your answers with those given at end of the unit.
(a) (i) Two important reactions of coordinated alkenes, resulting in new
alkenes are :
(x) ............................................
(y) ............................................
233
(ii) The ease of substitution of alkynes is .....................< .......................
<................ <.................
(x) .....................................
(y) .....................................
234
6.5 LET US SUM UP
After going through this unit you would have achieved the objectives
stated earlier. Let us recall what we have discussed :
235
Organo – copper, especially lithium dimethyl cuprate has been proved an
important reagent in organic synthesis. Its important reactions are :
236
Coordinated alkynes react with both nucelophilic and electrophilic
reagents. When they are coordinated with metals in their lower oxidation
state, they react with electrophiles; but when they are coordinated with
metals in their higher oxidation states they react with nucleophilic
reagents.
The important reactions of coordinated allyls are : (i) Insertion (ii) Metal
– exchange, (iii) Halide exchange, (iv) displacement and (v) Nucelophilic
reactions.
237
(iii) 1, 9 dimethyl p-quinone acetate
(v) ester
(y) dismutation
(ii) Acetylene < alkylacetylene < arene acetylene < nitro acetylene
(iv) - lactone
(ii) Ce4+
Cubane
(iii) ethyl
aromatic
(5-C5H5)
fission
(iv) arene
Fridel - Craft
238
M.SC. (FINAL) CHEMISTRY
BLOCK-III
239
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
Block-III : Summary
240
UNIT – 7 HOMOGENEOUS CATALYSIS – II : HOMOGENEOUS
CATALITIC PROPERTIES OF TRANSITION METAL
ORGANOMETLLICS
Structure
7.1 Introduction
7.2 Objectives
241
7.1 INTRODUCTION
7.2 OBJECTIVES
242
organotransition metal complexes in industrially important reactions, and
243
The important processes used in these steps are given below:
7.3.1 Oxidative Addition
Oxidative addition (or oxad) reaction which are useful for establishment
of new transition metal-carbon -bonds involve the oxidation (i.e., increase in
the formal oxidation number), accompanied by an increase in the coordination
number of the central metal atom. Complexes of metals in low spin d7, d8, or d10
configurations generally undergo this type of reaction and in the process of
enhancing their coordination number, the central metal tends to attain the stable
closed-shell configuration corresponding to 18 valence electrons.
244
The oxidative addition reactions have assumed special importance in
catalytic processes and this is generally the initiating step in a catalytic process
and involves the formation of bonding of some kind (, other delocalized
type) between the transition metal and the organic/inorganic substrate (through
oxidative addition or coordination); this is generally a key step in the catalytic
or / and stoichiometric process, e.g.:
245
most active and versatile catalysts known so far. In this connection, it may be
noted that coordinative unsaturation is generally guided by the 18-electron rule
(or effective atomic number rule). For example, metal complexes with 18
electrons in the valence shall are coordinatively saturated, irrespective of
coordination number, and therefore catalytically ineffective, e.g.,
IrCl(H)2(PPh3)3(d6), Fe(CO)5(d8), etc., whereas species with 16 electrons or less,
such as RhCl(PPh3)3 are coordinatively unsaturated.
In five coordinated (d8) metal complexes, vacant sites can also arise by
dissociation of one or more ligands either thermally or photochemically e.g.,
(-PPh3, heat) (-PPh3)
RhH(CO)(PPh3)3 RhH(CO)(PPh3)2 RhH(CO)(PPh3)
246
the following equation, hqas been extensively studied in view of it involvement
in catalytic reactions:
For example, the addition of methyl iodide to the rhodium (I) complex,
RhI2 (CO)2 is a key step in the Monsanto acetic acid synthesis; in the initiating
reaction rhodium is oxidized from + 1 to + 3 oxidation state:
247
grounds. However, the development of metal vapour and reactive metal
production techniques have added new dimensions in this particular area.
248
(d) Electronic nature of the Ancilliary Ligands
The presence of ancilliary ligands which enhance the electron density around
the metal atom in a complex also influences the course of the reactions. For
example, RhCI(PPh3)3 undergoes facile oxidative addition, but RhCI(CO)
(PPh3)2 is much less active for oxidative addition. The replacement of one
strongly donor and weakly acceptor PPh3 ligand in RhCl (PPh3)3 by a weakly
donor and strongly acceptor CO ligand should result in a lower electron density
on the central rhodium atom in the latter complex, RhCI(CO) (PPh 3)2 and thus
explain the difference in reactivity of the two complexes, although a steric
factor is another parameter to be considered. In a series of isosteric triaryl-
phosphines in the Wilkinson complex, the observed order of hydrogenation
activity: (p-CH3OC6H4)3P > (C6H5)3P > (p-FC6H4)3P can be explained on the
basis of the variation in the donor capability of the three ligands.
249
Alternatively, electronic activation of carbon-carbon bonds in molecules
like dimethyloxalate and cyanogen can facilitate the cleavage reactions:
(a) Insertion:
250
(i) Insertion of carbon monoxide. The CO insertion products are especially
important, as they appear to be key intermediates in a variety of catalytic
and industrial processes, such as hydroformylation reaction:
251
(Where Cp=(5-5H5)
(Cp*=(5-C5Me5)
252
Another interesting feature of carbon monoxide insertion is the regio-
selectivity which is observed when two different hydrocarbyls are present, as
for example, in ZrRR'(5-C5H5)2 (where R/R' = CH(SiMe3)2/Me, Ph/Me,
CH2SiMe3/CHPh2):
(5-C5H5)2 ZrMe{CH(SiMe3)} + CO
(5-C5H5)2 ZrMe{2-COCH(SiMe3)2}
The CO molecule which assumes acyl character is not the external one, but it is
one of the CO groups already coordinated to the metal. Interstingly, the
incoming CO molecule occupies a position 'cis' to the acyl group.
253
step consists in the following type of conversion:
254
A few typical examples of such insertion reactions are given below :
255
Although products from SO2 insertion into transition metal-carbon
bonds can also vary, yet the usual product is S-sulphinate:
M – R + SO2 M(SO2R)
78 0 C
TiMe ( 5 - C H ) 2SO Ti (1 O SMe) ( 5 C H )
5 5 2 2 2 2 5 5 2
O bonded
The selective insertion of SO2 into a gold methyl rather than a gold
256
phenyl bond in the last reaction indicates that SO2 does not act as a simple
electrophilic reagent. Rather coordination of SO2 to gold followed by alkyl
transfer is considered more plausible.
By contrast, SO2 insertion into the Co-R groups of cobaloximes, has been
explained, on the basis of a radical chain mechanism:
Co – R Co0 + R0
257
(iii) Insertion of isocyanides (RNC): Although isocyanides are isoelectronic
with CO, yet examples of their insertions into the transition metal – carbon
bond are relatively fewer in number. Few examples of isocyanides insertion
reactions are:
258
b) Elimination:
These reactions in most cases are the reverse of insertion reactions. As the name
signifies, this class of reactions involves elimination of a molecular species
from appropriate complexes with or without change of oxidation state of the
central metal atom. The former type is accompanied with a lowering of the
oxidation state of generally an intermediates species involved in catalytic
processes. The latter type, involving elimination of molecules like N2, CO, CO2,
SO2 and H2 from appropriate species such as azoderivatives, acyls, carboxylates,
sulphinates and hydrides respectively, leads to the formation of a new transition
metal-carbon -bond as illustrated by the following typical examples:
(i) Azo-derivatives :
(ii) Acyls :
80 0 C CH2
(OC) 5 Mn CH 2 CH CH 2 HC Mn(CO) 4 CO
or hv CH2
Fe(COPh)(CO) 2 ( 5 C5 H 5 )
hv
Mn( Ph)(CO) 2 ( 5 C5 H 5 ) CO
250 C
Co(CF3 )(CO) 4 CO
259
(iii) Carboxylates
(iv) Sulphinates
heat
IrCl2 (C6 H 4 Me p)(CO)( PPh3 ) 2 SO2
(v) Hydrides
260
Some typical examples of alkene elimination reactions are illustrated below:
M-C≡O+Nu- [M-C(Nu) O] –
261
Chemisorptions of hydrogen on platinum metal and coordination of hydrogen in
iridium complex are also important.
As has been pointed out H2 molecule can co-ordinate with metal complexes
without breaking of H-H bond, eg. in [W (CO)3 (H2) (P'Pr3)2]. Now large
number of such compounds has been prepared. They may regard processors of
hydride complexes. MOT indicates that electron-density from H2 molecule is
transferred into vacant orbital of the metal. Simultaneously back bonding in -*
orbital of H2 takes place. Similar reactions may take with C-H and C-C bonds
e.g. intramolecular cyclometallation or orthometallation reactions of
262
coordinated PPh3 :
Ph P
263
Check your Progress-1
264
7.4 SOME HOMOGENEOUS CATALYTIC REACTINOS OF
INDUSTRIAL IMPORATNCE
265
The hydrogenation of naturally occurring materials/products (general or
at selected specific sites of unsaturation) with double bonds often leads to very
useful materials. In this direction, hydrogenation of vegetable oils to solid facts
can be cited as an important example. These hydrogenation reactions are
assuming ever-increasing importance due to their newer and novel applications
in petrochemical and drug industries. In these directions, useful heterogeneous
catalysts for specific purposes are Adams catalyst (platinum black oxide):Pd/C'.
Pd/BaSO4, Raney nickel, rhodium, ruthenium, and copper-chromium
oxide.Typical hydrogenations (using heterogeneous catalysts) have to be carried
out at moderately high pressures of hydrogen (~1000/psi) and generally at
elevated temperatures. Any catalysts capable of facilitating hydrogenation
reactions at ambient conditions, therefore, are obviously very attractive
propositions and in more recent years, homogeneous catalytic systems have
proved highly successful in these directions.
Fig. 7.1
266
Out of a large number of homogeneous hydrogenation catalysts or
catalyst precursors such as RhCI(PPh3)3; RhH(CO)(PPh3)2; IrCI(CO)(PPh3)2;
RuHCI (PPh3)3; Ru (H) (CI) (CO) (PPh3)3 and PtH (SnCI3)2,(PPh3)2 the first one
known as Wilkinson's catalyst continues to occupy a position of predominant
importance.
(the above indicates cis hydrogen addition and the same has been established by
'H and 31P n.m.r. spectroscopy; the coordination number of rhodium increases
from 4 to 6 and its oxidation state from +1 to + 3 and hence, the process is
known as 'oxidative addition' of hydrogen).
267
In addition to activation of hydrogen by a oxidative addition process
occurring with Wilkinson's catalyst, alternative routes, e.g. homolytic splitting
and heterolytic fission, have also been suggested for hydrogen activation; these
can be illustrated with the catalysts such as [Co(CN)5]3- (d7) and [RuCI6]3- (d5)
respectively.
hemolytic
3-
2[Co" (CN)5] + H2 2[Co'"H (CN)5]3-
splitting
heterolytic
3-
[RuCI6] +H2 fission [RuHCI5]3- +H+ +CI-
268
In view of the catalyst being regenerated after a cycle of reactions, it
should be possible to represent a catalytic process by a closed loop
incorporating various steps of reactions involved. For example, the above
reactions can be combined in a loop form as represented in Fig. 7.1.
(In spite of the higher stability of the 18-electron systems in general, the
tendency of the above dissociation can be understood on the basis of steric
relief brought about by the dissociation of a bulky triphenylphosphine, PPh3
ligand):
269
(Coordination of alkene to the metal atom polarizes the C-C bond and
allows facile migration of the alkyl with its bonding electron pair):
The unique features of above catalytic steps are (i) hydrogenation of alkenes by
RhH(CO)(PPh3)3 is unusual in its being highly selective for the hydrogenation
of alk-I-ene compared to alk-2ene; and (ii) hydrogenation follows anti-
Marknownikov rule.
270
plastics is a thermodynamically favoured process. However, the alkene must
first be activated by a catalyst, so that the polymeriazation reaction may proceed
at a reasonable rate. A variety of organometallic compounds have been
frequently used for this activation or catalytic process and the reactions in their
presented generally lead to stereoregular polymers. Stereoregular
polymerization leads to the arrangement of the repeating units in a stereoregular
arrangement and it may be interesting to point out that nature has been
accomplishing the same in an efficient manner all the time. Quartz; the
polysaccharides; starch and cellulose; and the polynucleotides: DNA
(deoxyribonucleic acid) and RNA (ribonucleic acid) are all the examples of
such natural stereoregular polymers.
(a) Isotactic polymer (In this all methyl groups lie on the same side of the
chain, which teds to adopt a helical shape so that the methyl groups do
not sterically interfere with one another)
271
(b) Syndiotactic polymer (In this, there is a regular alternation of methyl
groups along the chain)
high tempeature
nC2 H 4 C2 H 4 n
and pressure
The origional uncatalyzed industrial process for polythene involved the use of
high temperatures and pressures and the product was atactic, amorphous, and of
low density. However, K.Ziegler (Germany) and G. Natta (Italy) achieved low
pressure and room temperature stereoregular catalytic polymerization of
ethane and propane in the presence of organometallic mixed catalysts (1955)
to give isotactic, high density, harder and tougher, higher melting crystalline
272
polyethylene ("Polythene") and other plastics on an industrial. scale, for which
they shared Nobel Prize for Chemistry in 1963. A typical Ziegler-Natta
catalyst can be made by mixing TiCl4 and Al2Et6 in heptane. In Ziegler-Natta
type of catalytic system consists of a reducing and/or alkylating agent from
Group I-III such as an aluminium alkyl (usually Al2Et6 or AlClEt2)2, and a
transition metal compound (usually a halide of early transition metal series, e.g.
TiCl4, TiCl3, or VCl4) In fact, Ziegler cites the following rule: take any
organometallic combine it with a compound of a transition metal, and you will
have a good chance of finding a suitable catalyst for your special
polymerization problem"
273
(Fig 7.3.).
Due to the formation of an empty coordination site exposed at the surface of the
alkylated titanium (III) halide, a molecule of propylene (propene) can bind itself
to it through it -electrons (step 2) :
274
This reaction brings the alkyl group and the alkene in proper stereochemical
arrangement to facilitate migration of the alkyl group to alkene (i.e., cis-
insertion in the neighboring metal-alkyl bond), giving a longer chain (i.e.,
growing polymer chain) of the alkyl derivative; this results in a fresh vacant site
at the surface (step 3) :
This vacant site can be occupied by another propene molecule and the insertion
process is repeated and steps (2) and (3) continued until a chain termination
process occurs by the severing of the titanium-alkyl bond :
The vacant site can be occupied by another propene molecule and the insertion
process is repeated and steps (2) and (3) continued until a chin termination
process occurs y the serving of titanium-alkyl bond:
275
Alternatively, the process may be sometimes interrupted by -elimination of a
metal hydride or by hyrolysis :
276
Besides the above two, another view of the possible mechanism which is
currently emerging is based on C-HTi interactions (for which Green and Co-
workers have proposed the term "agostic", to illustrate especially those
situations in which hydrogen atom is covalently bonded simultaneously to both
a sp1 carbon atom and to a transition metal atom).
277
H
Cl 2 Ti C has been actually observed in the X-ray structure
H H
recorded recently (1982) of TiCl3CH3 (dmpe).
The role of the cobalt catalyst, CO2(CO)8 can be illustrated by a catalytic cycle
shown in Figure 7.4 :
278
Fig. 7.4. Catalytic Cycle for hydroformylation of alkenes by cobalt catalyst.
(a) volatile nature of CoH(CO)4 leading to its loss along with the product
aldehyde and requiring its separation which is generally done in the
form CoSO4.
279
A comparative perusal of these hydroformylation and hydrogenation
reactions shows their mechanistic similarity. A number of catalysts like
RhH(CO)(PPh3)3 can, therefore, be effective in both types of reactions.
More recently it has been found that the platinum group complexes such
as RhCl(CO)(PPh3)3, RhH(CO) (PPh3)3 and Ru(CO)3(PPh3)2 are much more
effective than cobalt complexes. These new complexes facilitate the reactions
much more effectively to proceed at lower temperatures and pressures.
280
emphasized that the conditions for any reaction at the industrial scale are
chosen in a manner so that the process has an optimum economic feasibility.
281
Fig.7.5 Catalytic cycle for the hydroformylation of alkence
(p*represents PPh3)
282
ketone. It has been stated that "the invention of the Wacker process was a triuph
of common sense". It may be noted that the oxidation of ethylene to
acetaldehyde with the help of platinum group metals had been known as for
back as 1894:
heat
[PtCl3(C2H2)] + H2O CH3CHO + Pt (O) + 3Cl
-
Zeise's salt
It was, however, more than six decades later that Smidt working at
Wacker Chemie laboratories discovered a practical process for the oxidation of
ethylene to acetaldehyde using PdCl2 as a catalyst. For the mechanism of the
reaction, the following sequence of key-steps has been proposed on the basis of
extensive kinetic and other investigations:
[PdCl2(H2O)(C2H4)] [PdCl2(H2O)](C2H4OH)]-+H+
(d) β-Hydrogen elimination and (e) Migratory insertion into Pd-H bond.
283
(e) β-Hydrogen elimination
284
Fig. 7.6 : Wacker Process Catalytic Cycle
The role of copper (II) chloride in the Wacker process (Fig 7.6) appears
to be the regeneration of the catalyst [PdCl4]2 species by oxidation of Pd(O),
getting itself reduced to Cu(I) state which is oxidized by oxygen in the presence
of HCl back to the +2 oxidation state:
285
(ii) Catalyst, [PdCl4]2- regeneration,
Steps (a) to (f) in the suggested mechanism of the Wacker process can be
represented by a cycle (Fig. 7.6) in which the reactants entering and the
products leaving the system are indicated at appropriate place. By inclusion of
the reactions representing the catalyst and co-catalyst generation the cycle is
completed.
For the first time (H2/CO) mixture was prepared in the form of water-gas
by passing steam over red-hot coke. The ratio of hydrogen and carbon
monoxide can be changed using water gas shift reaction, in which reactants are
catalyzed using many homogeneous and heterogeneous catalysts.
286
C + H2O CO+H2
Hot + Steam Water gas
CO + H2O CO2 + H2
Now a days use of homogeneous catalyst has become very common, and
metal carbonyl complexex, such as {HFe (CO)4}, {Rh(CO)2I2}and {Ru (bpy)2
(CO) Cl}+ have been found very useful homogeneous catalyst for this reaction.
The scheme of the reaction catalysed using {Ru (bpy)2 (CO) CL}as a
homogeneous catalyst is shown in fig 7.7.
Fig. 7.7
287
converted into methanol:
CH4 (H O)
2 H2 + CO CH3OH
288
The bridged carbene of the dimetallic complex, which is analogous to
surface carbene of the heterogeneous catalyst (Fischer – Tropse Process), takes
part in formation of C-C bond.
(ii) Compare your answers with those given at the end of the unit.
289
(ii) Oxidation of alkene is known as ............................. or ............................
process. In this process ..................................... along with
......................... is used as a catalyst.
1. _______________________
2. _______________________
3. _______________________
4. _______________________
5. _______________________
6. _______________________
After going through this unit you would have achieved the objectives stated at
the start of this unit. Let us recall what we have discussed in the unit:
290
catalytic mechanish are as follows:
For oxidative additions, it is necessary that the metal ion must possess
vacant coordination place and also should have suitable orbital for
bonding.
(iii) Higher strength of the newly formed bond (M-X), compared to that
of the breaking bond (X-Y)
291
In cases of agostic association (behaviour of C-H as ligand), oxidative
addition takes place through intermolecular cyclometallation or
orthometallation process.
Many transition metal ions, viz Ru(III), Ru(II) Co(II), Co(I), Rh(I),
292
Ir(I) , Pd(II), Pt(II), Ag(II), Ag(I) and Cu(I) reduce activation energy
of hydrogenation reaction and catalyse it.
293
catalyses polymerisation of alkene in continuous insertion steps. The
insertion takes place before the coordination on electrophilic center-
Zr.
In the last, step VI- Mobile insertion releases an aldehyde and the
catatlyst is regenerated.
294
1. Elimination of Lewis base, PPh3
3. Ligand association
5. Ligand Association
6. Oxidative addition
7. Reductive elimination
4. β-Hydrogen elimination
295
Synthetic gasoline is being prepared from synthesis gas (H 2+CO)
using heterogeneous catalyst.
(ii) elimination
primary step
bonding
reactants
metal ion
suitable orbital
296
metal ion
receptive
do not
receptive
margarin, pharmaceuticals
petrochemicals
tricoordinated Complex
oxidative addition
the alkene
297
alkane
electrophilic – Zr
coordination.
CoH (CO)4
(ii) oxopalladation
Wacker Process
PdCl2
CuCl2
4. - hydrogen elimination
298
5. Mobile insertion in Pd-H bond
(iv) homogenous
ZSM – 5
methanol
gasoline
299
UNIT – 8 FLUXIONAL ORGANOMETALLIC COMPOUNDS
Structure
8.1. Introduction
8.2. Objectives
300
8.1. INTRODUCTION
No molecule is strictly regid even at 0 K due to the interatomic vibrations, but the amplitude
of vibration about mean position is about 10-30 pm. However, some molecules, like PFs,
some metal carbonyls and organometallics, called fluxional molecules, undergo
deformational rearrangements in which the atoms actually interchange their places with one
another. In case of PF5, for example, rapid exchange of the axial and the equatorial fluorine
atoms in the trigonal pyramid structure through the intermediate square pyramid (>105 5-1)
makes the NMR spectrophotometer record all the fluorine atoms in an identical environment
which is the weighted average of that prevailing in the separate environments (Fig. 8.1.).
Because of the small difference in the energies, the 5-coordinate (TBP→SP→TBP) and the
8-coordinate complexes (square antiprism→ dodecahedron→square antiprism) are generally
fluoxinal even at low temperature.
In this unit we shall analyse different transition metal organometallic compounds for
fluxional behaviour.
8.2. OBJECTIVES
The main aim of this unit is to analyse different transition metal organometallic
compounds for their fluxional behaviour. After going through this unit you should be able to:
301
are ofcourse continuously involved in approximately harmonic vibration about their
equilibrium positions, but in other respects the structures may be considered rigid.
In other words, if the two or more configurations are equivalent (in structure, bonding
and energy content). Such molecules are called fluxional (name suggested by Doering and
Roth, 1963).
In systems such as PF5 and Fe (CO)5 fluxional behaviour was first detected. In 19and
13
C n.m.r. spectra respectively of the above two molecules, only one resonance peak was
observed instead of two in the ratio of 3:2 (i.e. ratio of axial to equatorial sites).
302
From theoretical considerations, it can be concluded that when two nuclei, the
resonance frequencies, of which differ by (v1-v2)= v/sec., change site at a frequency higher
than (v1+v2)/sec., then only one resonance peak would be observed at the mean (v1+v2)/2
position of the two frequencies characteristic of two types of sites, between which
interchange is occuring.
303
equivalent to one another. The sp configuration (b) could return to the original tbp
configuration (a), or go a step further to attain the new tbp configuration (c) in which the
molecules have effectively rotated round the F3P axis through 90º. In view of this apparent
rotation. Berry mechanism is termed 'pseudorotation.
The next observation relevant to this field was the observation of a single 13C peak in
the n.m.r. spectrum of Fe(CO)5, which according to the two plausible structures, trigonal
304
bipyramid (tbp) and square pyramid (sp), was expected to give two signals in the ratios of 2/3
or ¼ respectively. The observation about the appearance of only a single peak was confirmed
by Nyholm and coworkers (1962) who believed in the 'sp' structure contrary to the 'tbp'
structure assumed by Cotton and coworkers. Incidentally, the structure in the solid state has
been established (1974) by X-ray crystallography to be of the 'tbp' type.
Out of the different spectroscopic tools (microwave, infrared, and nuclear magnetic
resonance spectroscopy), the n.m.r. technique has proved to be of maximum utility in the
study of fluxional behaviour. For a number of systems, the speed of rearrangement is fast
enough at the ambient temperatures for the n.m.r. techniques not be able to detect the same,
but at lower temperatures the rearrangements become slow enough to be detected by n.m.r.
spectroscopy (Table 8.1).
Table 8.1
Time scale for selection of the method for study of structures
The choice of a technique suitable for the study of a fluxional system would
305
obviously depend on the rate of rearrangements in a specific case. From this point of view,
the spectroscopic techniques could be divided into two broad groups.
(a) In some fast techniques like electronic and vibrational spectroscopy and gas phase
electron diffraction, the act of observing the molecule is completed in <10-11 sec.
Process of rearrangement are generally not fast enough to influence these
observations. Thus by these techniques, (i) no fluxional behaviour would be expected
to be observed if the different configurations are equivalent and (ii) for tautomeric or
isomeric molecules, both forms will register their presence in the spectrum, but no
indication of the inter conversations could be possible.
Normally, studies of fluxional molecules are carried out with the following two main
objectives:
(i) establishing definitely the instantaneous structure (for which information can
be achieved by recognising the limiting spectrum) of the molecule; and
These targets can be conveniently achieved by n.m.r. line shape analysis and this
technique will, therefore, be discussed in some detail.
306
8.4. FLUXIONAL BEHAVIOUR OF 2-OLEFIN COMPLEXES
Alkenes are in general rigidly bonded to the transition metals and these complexes
are, therefore, often fluxional in nature. As discussed nmr (particularly'H) studies provide an
insight into such behaviour of complexes in solution. It has been found that the solid state
structures do not often persist in solution and these studies, therefore, assume special
importance in such cases where complexes are used in solution state in their industrial
applications. Non-rigid attachment of alkenes to transition metals generally permits rotation
either of a barrel-type (i.e. the rotation of metal- alkenes axis).
307
In addition to the explanation of the nature of the variable temperature n.m.r.
spectrum observed for the molecule on the basis of rotations another possible interpretation
could be on the basis of intermolecular exchange of ethene molecule. The latter possibility is,
however, ruled out by the high rhodiumethene dissociation bond energy which has been
separately measured as~130kJ mol-1.
A study of the variable temperature n.m.r. study of the molecule, (Fig. 8.3) helps to
distinguish between the two types of rotation. The 1H n.m.r. spectrum of the molecule at-
90ºC does show two sets of resonance lines of equal intensity (one for two ethene protons
closer to CO and the other for the two protons in the proximity of NO), but these coalesce to
a broad signal at-65ºC. However, compared to the simple complex, (5-C5H5) Rh (C2H4)2 this
31
osmium complex (8.4) incorporates two PPh3 ligands also, the P atoms of which begin to
show spin-spin coupling with the four equivalent ethene protons at still higher temperatures
to give a triplet with intensities in 1:2:1 ratio. This coupling between protons and phosphorus
atoms is observed in higher temperature spectrum. This observations lends support to B
13
rather than A type rotation. These conclusions are further corroborated by the C spectrum,
which shows for the ethene ligand at 20ºC only one 13C line, which splits into two equivalent
lines when the temperature is lowered.
Fig. 8.4
308
converted into only one peak, which shows all the hydrogen equivalent. This is probably due
to the transient configuration during mobility of iron atom in alene -system. (Fig. 8.5).
Fig.8.5
A few compounds of cyclic alkenes, in which free alkene ligands has more -
electrons available than the number required to satisfy the 18 Electron or Effective Atomic
Number Rule, are listed below:
W(CO)3(4-C8H8); Co(4-C8H8)(5-C5H5);Fe2(CO)5(3-C8H8);
Mn(CO)3(5-C7H7);Mn(CO)2(2-C8H8)(5-C5H5);Fe(CO)2(2-C8H8) (5-C5H5);
Ru(CO)3(4-C8H8);and Nb(5-C5H5)2(2-C7H9).
It has been shown by n.m.r. spectroscopy that in solution these molecules generally
undergo rapid intramolecular rearrangement which is recognized by fewer lines in the
spectrum than one would expect for the static molecule.
The 'H n.m.r. spectrum (Figure 8.6) of Fe(CO)3(4-C8H8) consists of only a singlet
(5.2) at room temperature which splits to give two broad signals (as shown in Fig. 8.6 at-
309
45ºC. The spectrum is of A2H2M2X2 type with two peaks of almost equal intensity indicating
that eight alkenic protons can be divided into two equal groups of four coordinated and
another four uncoordinated ones:
There has been considerable controversy regarding the assignments of the two signals
in the above spectrum as well as on the actual instantaneous structure and the rearrangement
pathway.
This structure has been supported by X-ray structural determination confirming that it
is of the (1,3-diene) metal type. Keller and coworkers (1966) have however, argued in favour
of a dynamic exchange (Fig. 8.8)
Cotton and coworkers (1966), on the other hand, have suggested a static tub-bonded
310
C8H8 structure (Figure 8.9); in which coordinated alkenic protons give rise to the high field
signal.
Cotton's suggestions have received support from a study of the n.m.r. spectrum of
methyl –d-cyclooctatetraene-2,3,4,5,6,7-d6-iron tricarbonyl by Anet and coworkers (1967),
who showed that the terminal and internal protons of the 1,3-diene moiety coordinated to
iron show little difference in chemical shift. In spite of evidence cited above for Cotton's
structure (Fig. 8.9), some more data have been accumulated favouring structure 8.7 also. The
story, therefore, is still incomplete and requires more refined and penetrating measurements
as well as interpretations.
With the intuition that the behaviour of ruthenium complex would be similar to that
of its iron analogue and rate of rearrangement may be slower, Cotton and coworkers (1969)
prepared and studied the complex Ru(CO)3 (4-C8H8). The observed spectra are
demonstrated in Figs. 8.10.
311
The spectra of Ru(CO)3(4-C8H8) at the lowest temperatures are essentially limiting
spectra (even spin-spin hyperfine structure may be seen), and demonstrate fully without
anomalies or ambiguities that the instantaneous structure is of the 1,3-diene metal type. The
technique of computer simulation of spectra was employed to ascertain the rearrangement
pathway. Out of various possible pathways (e.g.1,2-;1,3-;1,4- and random shifts), the
computed spectra for the except 1.2 shifts were in gross qualitative disagreement with the
observed specta. For the 1,2-shifts, the agreements is very close, as comparison of Fig. 8.10.
and 8.11 will show.
Zr( 3 C3 H 5 ) 4 ; Cr ( 3 C3 H 5 ) 3 , Ni( 3 C3 H 5 ) 2 ;
312
Zn(3-C3H5)2 are known. In these complexes, the instantaneous structure may be
represented either by localized -bonding (Fig.8.12.a) or delocalized -bonding. (8.12.b)
In the -complex (8.12.a), the two hydrogen atoms on - and -C atoms would be
magnetically equivalent to each other. However, for 3-allyl complexes (8.12.b).
which are rigid on the 'Hn.m.r. time-scale, the syn and anti hydrogens
(Hb and Ha) both exhibit a doublet due to the coupling with the central hydrogen (Hc) which
shows a multiplet. Typical n.m.r parameters observed are : He, 6.5-4; Hb, 5-2.5; Ha, 3-1;
J7Hz, Jac 11 Hz, and Jab 0Hz.
The -allyl group often behave as an electron-rich moiety, but in some of these
reactions there appears to be prior dissociation of one terminus to form an intermediate -
allyl moiety. This kind of system is often reversible and fairly facile, leading to fluxional
rearrangement on the 'Hn.m.r. time scale.
In the -allyl system there is free rotation about the carbon-carbon single bond, so that fascile
groups. 3 to 1 rearrangement provides a mechanism for exchanging the syn an anti groups.
It my be noted that the transformation 3 to 1 ( to ) allyl creates a vacant coordination site
on the metal. The rearrangement of to form undoubtedly accounts for the wide range of
reactivities shown by metal allyl complexes.
313
The complex Mn(CO)4 (3-C3H5) can exyhibit a rigid 'H n.mr. spectrum such as that
shown in Fig. 8.12.
The spectrum shown is of AA'BB'X type where, in the case of the 3-allyl metal
complex. X is the proton on the central carbon atom, A and A' are protons (quite different
from X) and are located anti to X, and B and B' are protons again quite different from X but
similar to A and A' and located syn to X. At elevated temperatures or in the presence of a
base, however, this spectrum collapses to a dynamic A4X spectrum, the chief feature of
which is change of the doublets for the A and B protons to a single doublet presumably
owing to a rapid (on the n.m.r. time scale) intramolecular rearragement that causes the A/A'
(anti) and B/B' (syn) protons to have the same chemical shift.
Trihaptoallyl-metal complex
Fig. 8.12.
314
This transition may be represented as follows :
Fig. 8.13.
Fe(1-C5H5)2(5-C5H5);Cu(1C5H5)(PEt3);Si(1C5H5)Me3; Ge(1C5H5)2;
Re(1-C7H7)(CO)5,
315
The Compound Fe(1-C5H5)(NO)2(5-C5H5)(first synthesized by Piper and
Wilkinson in 1953) represents one of the first examples of fluxional organiometallic
molecules. The observation of two singlets in the 'H n.m.r. spectrum (at room temperature)
was considered to be highly unusual, because one would expect a singlet (for pentahapto
cylcopentadienyl ring) and a pair of doublets (for monohapto cyclopentadienyl ligand) or
triplets. Such observations in the 1H n.m.r. study of Fe(1-C5H5) (CO)2 (5-C5H5) and for
many other similar systems. (fig 8.14) led to a conjecture about a mechanism for
rearrangement reactions which could render all the monohapto bonded cyclopentadienyl
protons magnetically equivalent. The variable temperature. 1H n.m.r. spectrum of this
molecule (Fig. 8.15) over the range + 30oC to ─100oC provides valuable information. Some
characteristic features of the spectrum are: (i) the nature of the spectrum over the range
─80oC to ─100oC is almost unaltered (the limiting spectrum) and provides evidence
regarding the instantaneous structures in solutions, and (ii) recognition of rearrangement
pathway.
Fig. 8.14.
(a) NMR at -270C
(b) NMR at -620C
316
Fig. 8.15. The variable temperature 1Hn.m.r. spectra (at 60 HMz) of
Fe(1-C5H5)(CO)2(5-C5H5) in CS2
Although the plausible pathways for proton averaging may involve (i) a dissociative
mechanism, (ii) random shifts, (iii) 1,2-metal shift (i.e. movement of a metal atom around the
cyclopentadienyl ring from one carbon to the carbon α to it), or (iv) 1, 3-metal shift, yet the
experimental evidence favours the 1, 2-metal shift as the most appropriate mechanism (Fig
8.16)
317
(but not a mixture of both). A close examination of the spectrum (Figure 8.14) permits one to
distinguish between the latter two pathways provided the two low-field complex multiplets
can be assigned;
(ii) Multiplets in the low-field may be described as AA'BB' resonance, the downfield side
of which is broadened more by interaction with allylic H compared to the upfield side; this
may be due to α-H atoms. It may be noted that assignment of α- and β-character on the basis
of chemical shifts is highly risky. However, magnitudes of coupling constants would be
fairly safe to indicate α- or β-character of the protons, e.g. α-protons would be coupled (with
a coupling constant value 2Hz) more strongly to allylic H than the β-proton (J0.5 Hz). In
view of the above, the downfield part of the multiplet, which collapses faster than the upfield
half, may be considered to have predominantly α-character, and the rearrangement pathway
would involve more frequent in and out movements of protons in the α-environments than in
the β-environment. It is easy to recognize that a succession of 1, 2-shifts causes redistribution
of protons among α-environments, twice as often as among β-environments (whereas 1, 3-
shifts have just the opposite effect).
An another important example is that of (5-C5H5)2 Fe2 (CO)4. At -70oC, the solution
of the complex show protons at two places in its 1H n.m.r/ spectra, which with the increase in
temperature converts into single strong signal (Fig 8.17)
318
13
C n.m.r. shows cis-trans exchange in this complex (Fig 8.18) between bridged and
terminal CO groups:
Fig 8.18
(2) Compare your answers with those given at the end of this unit.
(iii) The most important method for the study of fluxional behaviour is
......................................................................... .
(b) (i) In NMR spectra of Os (PPH3) (CO) (NO) (C2H4) at ........................ temperature
........................................... of resonance lines of equal frequency are obtained,
which at ...................................temperature is converted in
to.........................................
319
.................................. trans. hydrogen's and ............................... ............... placed
perpendicular to six C-Fe bonds. On increasing the temperature these are
change to ........................................... showing that .............................................
13
(vi) C-n m r spectra of (n5-C5H5)2 Fe (CO) indicates .........................
..................... exchange of ................................. and CO groups.
After going through this unit you would have achieved the objectives stated earlier
in this unit. Let us recall what we have discussed so far:
The molecules which have more than one thermally accessible structures, which
under suitable conditions (specially temperature) are interconvertible from one to
another fairly rapidly. This phenomenon may be termed as fluxional behaviour.
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phenomenon was called berry`s pseudoratation.
As the diffraction and spectral (1R, Visible, UV) methods are quite fast (~10-14 to
10-20s) compared to molecular vibration, hence these methods are not useful for the
study of fluxional behaviour of compounds.
NMR. method was found quite useful in the study of fluxional behaviour of
molecules. In this method, changes in structures of n.m.r. lines, with the temperature
are analysed. Using this method fluxional of behaviour many organometallic
compounds has been studied e.g. 2-olefin complex, alene complex, π-bonded cyclic
alkene, complex.
3-allyl complexes and diene complexes.etc.
NMR spectrum of Os (PPh3)2 (CO) (NO) (C2H5), at -900 C shows two sets of
resonance lines of equal intensity, but these coalesce to a broad signal at -650C.
Showing the two sets of hydrogen in different environments at -650C.
At normal temperature Cp2 Hg shows three types of hydrogen in its n.m.r. spectra,
which changes, showing all hydrogen equivalent, at – 700C Similarly, 13
C-nmr
spectra of (5-C5 H5)2 Fe (CO) 2 shows that in the molecule there is cis-trans
exchange in between bridged and terminal CO-groups.
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8.8 CHECK YOUR PROGRESS : THE KEY
(a) (i) The molecules which have more than one thermally accessible structures, which under
suitable conditions (specially temperature) are inter convertible from one to
another fairly rapidly This phenomenon is known as fluxional behavior.
TBP
NMR
-650C
a broad signal
three cis
three
three hydrogens
single signal
(iii) 1,3
1,2
(iv) ligand
fluxional behavior
stereochemically
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XA4
two sets
(v) three
(vi) cis-trans
bridged
terminal
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