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Synthesis and Characterization of Copper (II) Complexes of Diamines and Cyanide

Name:

Javed Hussain Shah

Registration Date:

Part time/full time : Full time

Supervisor:

Chemistry Department University of Engineering and Technology, Lahore

Session: 2012-2014

Problem Statement:
Copper coordination chemistry involving a variety of nitrogen ligands, is of fundamental importance in chemistry, biology and materials science [1]. In this study, we plan to prepare Copper (II) complexes using diamines and cyanide as ligands. The characterization of the prepared complexes will be carried out by Melting Point, IR Spectroscopy and X-rays crystallography.

Introduction:
Efforts have been made to design and the preparation of mixed ligand complexes of Copper (II) complexes with diamines and cyanide [2,3]. Copper is essential for the occurrence of many processes in bioorganisms. Hence there is a huge number of works investigating biological activity of the copper ions and their interactions using both experimental and theoretical approaches. Copper cation interactions with diamines were investigated in studies [4-13] using various computational approaches. Experimental measurements, which were published, e.g., in [14-17] initiated some of these studies and were basically confirmed or some of their conclusions were explained by theoretical works. Very prosperous is the exploration so-called blue proteins , a group of electron transfer systems characterized by a bright blue colour, a narrow hyperfine splitting in the electronic spin resonance spectra and specially high reduction potential. Finally, copper plays an important role in many enzymayic processes [18]- e.g cytochrome c oxidase, lactase [19], Cu-Zn superoxidase dismutase. Present study is based upon the preparation of mixed ligand complexes of Copper (II) complexes with diamines and cyanide. Fortunately, the mixed-ligand strategy, is an

effective method for constructing metal-organic frameworks, allows tuning the coordination ability of ligands to corporately bind with metals centers. To further explore the coordination behaviour of diamines and cyanide, in the present work the Copper (II) complexes with diamines and cyanide will be prepared and characterized using different techniques.

Objectives:
The primary objectives of this research are as follows Preparation of Copper (II) complexes with diamines and cyanide . Characterization of the prepared complexes by M.P, IR spectroscopy. Crystallization of as many compound as possible and determination of their structures by X-rays crystallography.

A comparative study of complexes based on spectroscopic and structural data.

Literature Background:
Several groups have studied the coordination behaviour of diamines and cyanides towards Copper. A series of copper complexes with diamines and cyanides under different concentrations and under different conditions, have been synthesized. The mode of attachment of diamines with copper metal largely depends on other ligands. Large number of substituents attached, large steric hindrance favours M-N attachment of diamine ligands. Structural features were obtained from their elemental analysis, melting point, IR Spectroscopy and ESR spectral data of complexes suggest different geometries around the central metal ion. The reduction-oxidation behaviour of copper

plays an important role in copper complexes of diamines and cyanides. The nuclear activity of the metal complexes shows that Cu complexes cleave DNA through redox chemistry whereas other complexes are not so effective [20]. The present survey highlights structural properties and biological studies of transition metal complex derived from diamines and cyanide. The most important results of extensive studies (syntheses, spectral, magnetic, redox, structural characteristics, antimicrobial and DNA cleavage) of the metal complexes with diamines and cyanide.

Methodology:
(A) Preparation of complexes

Copper chloride solution will be prepared in water and the ligand diamines will be prepared in methnol but the cyanide ligand will be prepared in water . First of all, Copper Chloride solution will be mixed in diamine solution and stirred for 30-40 minutes. If clear solution will be obtained then cyanide solution will be mixed in it the and stirred for 15-30 minutes. The product will be separated by Filtration and crystallization.
(B) Characterization

The characterization of the prepared complexes will be done by using melting points, and IR spectroscopic techniques. Further the crystal structures will be determined by the X-rays diffraction techniques for crystalline compounds.
(C) Expected results

Some useful results are expected, which will be published in the well reputed international journals.

Research time table:

Literature Survey:

Feb. 2013

Experimental synthesis:

March - August, 2013

Experimental Characterization:

August - November, 2013

Thesis Writing:

November - December, 2013

Submission:

January, 2014

References:
[1]- S.J. Archibald, Comprehensive Coordination Chem II 6 (2004) 1147. [2]- B. Moulton, M.J. Zaworotko. Chem. Rev., 101, 1629, (2001) [3]- M. Eddaoudi, D.B. Moler, H.L. Li, Chem, T, Reineke, M. O keeffe, O.M. Yaghi. Acc. Chem. , Res., 34, 319, (2001). [4]- S.J. Archibald, Comprehensive Coordination Chem II 6 (2004) 1147. [5]- B. Moulton, M.J. Zaworotko. Chem. Rev., 101, 1629, (2001) [6]- M. Eddaoudi, D.B. Moler, H.L. Li, Chem, T, Reineke, M. O keeffe, O.M. Yaghi. Acc. Chem. , Res., 34, 319, (2001). [7]- J. Sabolovic, C.S Tautermann, T. Loerting, K.R. Liedl, Inorg. Chem. 42 (2003) 2268. [8]- A. Katz, L. Shimoni-Livny, O. Navon, N. Navon, C. Bock, J. Glusker, Helv. Chim. Atca 123 (2003) 782. [9]- J. Sabolovic, K. R. Liedl, J. Am. Chem. Soc. 38 (1999) 2764. [10]- J.Bertran, L.Rodrigues-Santiago, M.Sodupe, J.Phys. Chem. B 103 (1999) 2310. [11]- L. Rulisek, Z. Havlas, J. Am. Chem. Soc. 122 (2000) 10428. [12]- S. Santra, P. Zhang, W. Tan, J. Phys. Chem. A 104 (2000) 12021. [13]- T. Shoeib, C.F. Rodriques, K.W.M. Siu, A.C. Hopkinson, Phys. Chem. Chem. Phys. 3 (2001) 853. [14]- R. Prabhakar, P.E.M. Siegban, J. Phys, Chem. B 107 (2003) 3944. [15]- D. Caraiman, T. Shoeib, K. Siu, A. Hopkinson, D. bohme, Int. J. Mass Spectr. 228 (2-3) (2003).

[16]- P. Manilkandan, B. Epel, D. Goldfarb, Inorg. Chem. 40 (2001) 781 [17] K. Shimizu, H. Maeshima, H. Yoshida, A. Satsuma, T. Hattori, , Phys. Chem. Chem. Phys. 3 (2001) 862. [18]- P.E.M. Siegbahn, J. Comp. Chem. 22 (2001) 1634. [19]- A. E. Palmer, D. W. Randall, F. Xu, E.I. Solomon, J. Am. Chem. Soc. 121 (1999) 7138. [20]- N.Raman, J. Dhaveethu, Rajs, A. Sakthivel.J. Chem. Sci., 119, 303-310, 2007.

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