SYNTHESIS AND BIOLOGICAL ACTIVITY OF BIURET AND DITHIOBIURET METAL COMPLEXES By SAIRA SHERZAMAN Regd. No. 99-GMDG-3040 (Session 2007- 2010) Department of Chemistry Faculty of Sciences University of Azad Jammu and Kashmir, Muzaffarabad, Pakistan SYNTHESIS AND BIOLOGICAL ACTIVITY OF BIURET AND DITHIOBIURET METAL COMPLEXES BY SAIRA SHERZAMAN Regd. No. 99-GMDG-3040 A Thesis Submitted in partial fulfillment of the requirement for the degree of Doctor of Philosophy In Inorganic Chemistry Department of Chemistry Faculty of Sciences The University of Azad Jammu and Kashmir, Muzaffarabad, Pakistan Certificate of Approval This is to certify that the research work presented in this thesis, entitled "Synthesis and Biological Activity of Biuret and Dithiobiuret Metal Complexes” was conducted by Saira Sherzaman under the supervision of Prof. Dr. Sadiq-ur-Rehman. No part of this thesis has been submitted anywhere else for any other degree. This thesis is submitted to the Department of Chemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy in field of Chemistry, Department of Chemistry, University of Azad Jammu and Kashmir, Muzaffarabad. Student Name: Saira Sherzaman Signature: ___________________ Examination Committee: a) External Examiner: Prof. Dr. Rashid Ahmad Signature: ___________________ Department of Chemistry University of Malakand, Pakistan. b) Internal Examiner: Prof. Dr. Sadiq-ur-Rehman Signature: __________________ Department of Chemistry University of Azad Jammu & Kashmir, Muzaffarabad Prof. Dr. Sadiq-ur-Rehman (Supervisor) Signature: __________________ Prof. Dr. Khawaja Ansar Yasin (Chairman) Signature: _________________ Prof. Dr. Muhammad Qayyum Khan (Dean) Signature: __________________ Prof. Dr. Azhar Saleem (Director, ASR) Signature: _________________ ii CERTIFICATION Certified that the contents and form of thesis entitled “Synthesis and Biological Activity of Biuret and Dithiobiuret Metal Complexes” submitted by Saira Sherzaman have been satisfactory for the requirement of PhD in Chemistry. SUPERVISORY COMMITTEE Supervisor: Prof. Dr. Sadiq-ur-Rehman ____________________ Department of Chemistry University of Azad Jammu & Kashmir, Muzaffarabad Member 1: Prof. Dr. Khawaja Ansar Yasin __________________ Department of Chemistry University of Azad Jammu & Kashmir, Muzaffarabad. Member 2: Dr. Muhammad Naeem Ahmed ___________________ Assistant Professor Department of Chemistry University of Azad Jammu & Kashmir, Muzaffarabad. External Examiner: Prof. Dr. Rashid Ahmad ____________________ Department of Chemistry University of Malakand, Pakistan. ____________________________ Chairman Department of Chemistry __________________________ __________________________ Dean Director Faculty of Science Advanced Studies & Research iii iv DEDICATION I would like to dedicate my thesis to my beloved husband Dr. Abdul Rehman for supporting me all the way and my kids. v CONTENTS LISTS OF SCHEMES ......................................................................................... xi LIST OF FIGURES ............................................................................................ xii LIST OF TABLES ............................................................................................. xiv ABBREVIATION...................................................................................... xvi ACKNOWLEDGEMENT ................................................................................ xvi ABSTRACT ......................................................................................................... xx Chapter 1 ................................................................................................................ 1 INTRODUCTION ................................................................................................ 1 1.1 BIURET, THIOBIURET AND DITHIOBIURET METAL COMPLEXES 1 1.2 BRIEF INTRODUCTION OF TRANSITION METALS ............................. 4 1.3 REVIEW OF LITERATURE......................................................................... 6 1.3.1 Background Synthesis of Biurets, Thiobiurets and Dithiobiurets .......... 6 1.3.2 Synthesis of Thiobiuret ............................................................................ 9 1.3.3 Transition Metal Complexes of Thiobiuret ............................................ 12 1.3.4 Synthesis of Dithiobiurets ...................................................................... 13 1.3.5 Transition Metal Complexes of Dithiobiurets ........................................ 15 1.4 APPLICATIONS OF BIURET THIOBIURET AND DITHIOBIURET .... 16 METAL COMPLEXES ...................................................................................... 16 1.4.1 Biological Applications…………………………………………………..16 1.4.2 Non-Biological Applications..................................................................... 21 1.4.2.1 Precursors for preparation of nanoparticles .................................. 21 1.4.2.2 As a precursor of heterocyclic compounds ................................... 22 1.4.2.3 Potential as extreme pressure lubricant additives ......................... 23 1.4.2.4 Use as a corrosion inhibitor .......................................................... 23 1.4.2.5 As floating aid ................................................................................ 24 1.4.2.6 As liquefying agents ...................................................................... 24 1.4.2.7 Use in textile industry .................................................................... 24 1.4.3 Agricultural Applications ....................................................................... 24 1.4.3.1 Insect growth regulator .................................................................. 25 1.4.3.2 Effect on seed germination and plant growth................................ 25 1.4.3.3 Antifungal activity......................................................................... 26 1.4.3.4 Herbicidal activity ......................................................................... 26 1.4.4 Miscellaneous Uses ............................................................................... 27 1.5 STRUCTURAL ELUCIDATION TECHNIQUES ..................................... 28 1.5.1 Infrared Spectroscopy ............................................................................ 28 1.5.2 NMR Spectroscopy................................................................................ 29 1.5.3 X-ray Crystallography ........................................................................... 30 1.5.3.1 Crystal structure determination ........................................................ 30 1.6 BIOLOGICAL STUDIES ............................................................................ 30 1.7 SCOPE OF STUDY ..................................................................................... 31 1.8 PLAN OF WORK ........................................................................................ 31 vi Chapter 2………………………………………………………………………… 33 2.1 CHEMICALS .................................................................................................. 33 2.2 INSTRUMENTATION ................................................................................ 35 2.3 GENERAL PROCEDURE (A) FOR SYNTHESIS OF BIURET, THIOBIURET AND DITHIOBIURET METAL COMPLEXES ...................... 36 2.4 SYNTHESIS OF THIOBIURET AND DITHIOBIURET NICKEL(II) COMPLEXES USING DIFFERENT AMINES ................................................. 38 2.4.1 Bis[1,1,5,5-tetra ethyl-4-thiobiureto]Nickel(II) 1 ................................. 38 2.4.2 Bis[1,1-diethyl-5-( benzylmethyl)-4-thiobiureto]Nickel(II) 2 ............. 38 2.4.3 Bis[1,1-diethyl-5-(3-hydroxypyridine)-4-thiobiureto]Nickel(II) 3 ...... 39 2.4.4 Bis[1,1-diethyl-5-(1-(2-furoyl)-pipraziyl)-4-thiobiureto]Nickel(II) 4 .. 40 2.4.5 Bis[1,1-diethyl-5-(4-nitrophenyl)-4-thiobiureto]Nickel(II) 5 ............... 40 2.4.6 Bis[1,1-diethyl-5-(aminobenzyl)-4-thiobiureto]Nickel(II) 6 ................. 41 2.4.7 Bis[1,1- diethyl-5-(2-hydroxy benzoamide)-4-thiobiureto]Nickel(II) 7 41 2.4.8 Bis[1,1-diethyl-5-(methyl benzyl)- 4-thiobiureto]Nickel(II) 8 ............ 42 2.4.9 Bis[1,1-diethyl-5-(dodecylamine)-4-thiobiureto]Nickel(II) 9 ............... 42 2.4.10 Bis[1,1-diethyl-5-(2,4-dinitrophenylhydrazine)-4-thiobiureto]Nickel(II) 10 .................................................................................................................43 2.4.11 Bis[1,1-diethyl-5,5-dipropyl-4-thiobiureto]Nickel(II) 11 .................... 43 2.4.12 Bis[1,1,5,5-tetramethyl-2,4-dithiobiureto]Nickel(II) 12 ...................... 44 2.5 SYNTHESIS OF BIURET, THIOBIURET AND DITHIOBIURET COPPER(II) COMPLEXES USING DIFFERENT AMINES............................ 44 2.5.1 Bis[1,1,5,5-tetra ethyl-4-thiobiureto]Copper(II) 13 ............................... 45 2.5.2 Bis[1,1-diethyl-5-( benzylmethyl)-4-thiobiureto]Copper(II) 14 ............ 45 2.5.3 Bis[1,1-diethyl-5-(3-hydroxypyridine)-4-thiobiureto)]Copper(II) 15 .... 46 2.5.4 Bis[1,1-diethyl-5-(1-(2-furoyl)-pipraziyl)-4-thiobiureto]Copper(II) 16 46 2.5.5 Bis[1,1-diethyl-5-(4-nitrophenyl)-4-thiobiureto]Copper(II) 17 ............. 47 2.5.6 Bis[1,1-diethyl-5-(aminobenzyl)-4-thiobiureto]Copper(II) 18 .............. 48 2.5.7 Bis[1,1- diethyl-5-(2-hydroxy benzoamide)-4-thiobiureto]Copper(II) 19 .................................................................................................................48 2.5.8 Bis[1,1-diethyl-5-(methyl benzyl)- 4-thiobiureto]Copper(II) 20 .......... 49 2.5.9 Bis[1,1-diethyl-5-(dodecylamine)-4-thiobiureto]Copper(II)