SYNTHESIS, SPECTROSCOPIC and BIOLOGICAL STUDIES of 3D TRANSITION METAL COMPLEXES with VARIOUS ANILINE BASED SCHIFF BASES HABIB H
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SYNTHESIS, SPECTROSCOPIC AND BIOLOGICAL STUDIES OF 3d TRANSITION METAL COMPLEXES WITH VARIOUS ANILINE BASED SCHIFF BASES Submitted By HABIB HUSSAIN (2008-Ph.D Chemistry-02) Supervisor Prof. Dr. Syeda Rubina Gilani DEPARTMENT OF CHEMISTRY University of Engineering and Technology, LAHORE-PAKISTAN (2015) Synthesis, Spectroscopic and Biological Studies of 3d Transition Metal Complexes with Various Aniline Based Schiff Bases HABIB HUSSAIN (2008-Ph.D Chemistry-02) Department of Chemistry University of Engineering and Technology, Lahore Supervisor: Prof. Dr. Syeda Rubina Gilani A dissertation submitted to the University of Engineering & Technology Lahore in accordance with the requirements of the degree of Ph. D in the Faculty of Science. (2015) II Synthesis, Spectroscopic and Biological Studies of 3d Transition Metal Complexes with Various Aniline Based Schiff Bases This Research Thesis Is Submitted To the Department of Chemistry, University of Engineering & Technology Lahore for the Fulfillments for the Degree of DOCTOR OF PHILOSOPHY In CHEMISTRY Approved on ________________ Internal Examiner: Signature: _______________________ (Supervisor) Name: Prof. Dr. Syeda Rubina Gilani External Examiner: Signature: ________________________ Name: ___________________________ Chairperson of the Department: Signature: ______________________ Name: Prof. Dr. Syeda Rubina Gilani DEPARTMENT OF CHEMISTRY UNIVERSITY OF ENGINEERING & TECHNOLOGY LAHORE III FORM FOR THE RELEASE OF RESEARCH THESIS FOR EXAMINATION Declaration by the Candidate I “HABIB HUSSAIN” declare that the thesis titled; “Synthesis, Spectroscopic and Biological Studies of 3d Transition Metal Complexes with Various Aniline Based Schiff Bases” is my own work and has not been submitted previously in whole or in part in respect of any other academic award. ___________________ _________________ Signature of Candidate Date I approved that the above thesis can be submitted for examination. ___________________ _________________ Signature of Supervisor Date (Prof. Dr. Syeda Rubina Gilani) IV IN THE NAME OF ALLAH The Most Gracious The Most Merciful V Dedicated To My Beloved Parents Brother and Sister Family and Beloved Wife VI ACKNOWLEDGEMENTS I am very thankful to Almighty Allah; the entire source of knowledge and wisdom; and His Prophet Muhammad (peace be upon him) who enabled me to complete this work. I would like to take this opportunity to thank all the people who helped and supported me throughout the past years. Firstly, I would like to thank Prof. Dr. Syeda Rubina Gilani for giving me the opportunity to work within her group and for the supervision, guidance and education that she provided along the way. It has been a great pleasure for me to work with many wonderful people in this research group: thank you to everyone for providing a great atmosphere in which to work and develop my chemistry skills. I have learnt a great deal during my PhD and I know that my experiences will stay with me long after leaving University of Engineering & Technology Lahore. I am thankful to Prof. Dr. Fazeelat Tahira, Dean of Sciences and Humanities, University of Engineering and Technology, Lahore for providing me this precious opportunity. I am also thankful to all worthy Professors of Chemistry Department, U.E.T Lahore for providing me guidance time to time when needed. Prof. Dr. Varinder Aggarwal, Dr. Jack Chen, Dr. Helen Scott and the staff of the NMR, Mass Spectroscopy and X-ray crystallography departments, University of Bristol, U.K and University of Malaysia deserve a mention for their efforts in analyzing the complexes in this thesis and their willingness to answer my questions. Determination of antibacterial activities of ligands and complexes was a part of my work so I am highly thankful to Dr. VII Farkhanda Jabeen, Department of Botany, University of Punjab Lahore who provided me lab, memorable working environment and facilities for the investigation of bacterial activities. I am also thankful to Dr. Tayyeba (S.O), Shahid Rehman (S.O) and uncle Imam din PCSIR Lahore for her guidance in spectroscopic analysis and Mr. Atif, Mr. Anwar Nadeem, Mr. Tanveer Ahmed, Mr. Dilshad, Mr. M. Anwar and Mr. Niamat laboratory staff University of Engineering & Technology Lahore for their help and memorable cooperation throughout in my project. I am very grateful to Zulfiqar Ali, Hajira Rehman, Imdad Hussain, Dr. Amin Abid, Dr. Faiz Rabbani, Dr. Asif Ali, Amir Khan, Mehmood Baig, Nabeel-ur- Rehman, Mudassar Khalil, Mudassir Abbasi, Anum Saleem, Sarah Rahman, M. Imran Pasha, Hafiz Yousaf and all the management of Superior Group of Colleges especially Prof. Dr. Abdul Rehman (CEO) for their skilled guidance and encouraging attitude throughout my research work. Here I remember Higher Education Commission of Pakistan and say special thanks for providing me research funds. Finally, I have to thank my Father, Mother, Brother Zaheer Hussain Bubak, Sister Narjis Khatoon Bubak, Wife Humaira Perveen and Love for their support over the years. I know that you have no idea what most of this thesis means but it still couldn’t have been written without you. Habib Hussain (2008-Ph.D Chemistry-02) VIII Author’s Declaration I declare that the work in this dissertation was carried out in accordance with the regulations of the University of Engineering and Technology Lahore. This work is original, except where indicated by special reference in the text. And no part of the dissertation has been submitted for any other academic award. All views expressed in the dissertation are those of the author and in no way represent those of the University of Engineering and Technology. The dissertation has not been presented to any other University for examination in Pakistan or overseas. Signed: …………………… Date: ……………………. IX Table of Contents Chapter 1 INTRODUCTION......……………………………………………………………1-25 1.1 Studies of Metal Chelates------------------------------------------------------------02 1.2 Schiff Bases----------------------------------------------------------------------------02 1.3 Importance of Schiff Bases----------------------------------------------------------03 1.4 Biological Importance of Schiff Bases---------------------------------------------05 1.5 Types of Ligands----------------------------------------------------------------------06 1.5.1 Mono-dentate Ligands-------------------------------------------------------06 1.5.2 Bi-dentate Ligands-----------------------------------------------------------06 1.6 Chelate Formation---------------------------------------------------------------------07 1.7 Stability of Schiff Bases--------------------------------------------------------------08 1.8 Methods for Preparation of Imines--------------------------------------------------08 1.9 Synthesis of Imines--------------------------------------------------------------------09 1.10 Synthesis of Imine Metal Complexes-----------------------------------------------10 1.11 Applications of Imine Metal Complexes-------------------------------------------12 1.11.1 Imine Metal Complexes used as Catalysts--------------------------------12 1.11.2 Use of Imine Metal Complexes in Oxidation Reactions----------------12 1.11.3 Use of Imine Metal Complexes in Hydrogenation Reactions----------13 1.11.4 Use of Imine Metal Complexes in Epoxidation Reactions--------------14 1.11.5 Use of Imine Metal Complexes in Polymerization Reactions----------16 1.12 Biological Activities of Imine Metal Complexes ---------------------------------16 1.12.1 Antimicrobial Activities-----------------------------------------------------16 1.12.2 Antifungal Activities---------------------------------------------------------17 1.12.3 Antitumor and Cytotoxic Activities----------------------------------------17 1.13 Photochromism and Thermochromism in Schiff Bases--------------------------17 1.14 Stability of Metal Complexes--------------------------------------------------------18 1.15 Reactions of Transition Metal Complexes-----------------------------------------19 X 1.15.1 Substitution Reactions -------------------------------------------------------19 1.15.1.1 Substitution Reactions in Aqueous Solvent-------------19 1.15.1.2 Substitution Reactions in Non-Polar Solvents----------19 1.15.1.3 Substitution Reactions in absence of Solvent-----------19 1.15.1.4 Substitution Reactions without Metal-Ligand Bond Cleavage----------------------------------------------20 1.15.2 Thermal Dissociation of Solid Complexes--------------------------------20 1.15.3 Oxidation-Reduction Reactions --------------------------------------------20 1.15.4 Catalysis -----------------------------------------------------------------------20 1.15.4.1 Heterogeneous Catalysis ----------------------------------21 1.15.4.2 Homogeneous Catalysis -----------------------------------21 1.16 Transition Metals used for Synthesis of Complexes------------------------------21 1.16.1 Copper--------------------------------------------------------------------------21 1.16.2 Zinc-----------------------------------------------------------------------------22 1.16.3 Nickel --------------------------------------------------------------------------23 1.16.4 Cobalt --------------------------------------------------------------------------24 Chapter 2 INSTRUMENTATION…………………………………………………………26-36 2.1 Melting/Decomposition Points------------------------------------------------------27 2.2 UV-Visible spectrophotometry------------------------------------------------------27 2.3 Infra-red (IR) Spectroscopy----------------------------------------------------------28