Schiff Base Metal Complexes Schiff bases are compounds created from a condensed amino compounds, which frequently form complexes with metal ions. They have diverse applications in biology, catalysis, material science and industry. Understanding these compounds, their properties, and the available methods for synthesizing them is a key to unlocking industrial innovation.
Schiff Base Metal Complexes provides a comprehensive overview of these compounds. It introduces the compounds and their properties before discussing their various synthesizing methods. A survey of existing and potential applications gives a complete picture and makes this a crucial guide for researchers and industry professionals looking to work with Schiff base complexes.
Schiff Base Metal Complexes readers will also find:
A systematic and organized structure designed to make information instantly accessible Detailed coverage of thermal synthesis, photochemical synthesis, and more Challenges with different methods described in order to help readers make the correct choice for their own work
Schiff Base Metal Complexes is a useful reference for organic chemists, materials scientists, and researchers or industry professionals working with organometallics.
Preface xi Part I Introduction 1 1 Historical Background 3 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 1.1 Introduction 3 1.2 Theories of Coordinate Bond 4 1.2.1 Valence Bond Theory 4 1.2.2 Crystal Field Theory 4 1.2.3 Molecular Orbital Theory 5 1.2.4 Ligand Field Theory 6 References 7 2 Classification 9 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 2.1 Ligands 9 2.2 Schiff Base 9 2.3 Types of Schiff Base 12 2.3.1 Salen-type Ligands 12 2.3.2 Salophen-type Ligands 12 2.3.3 Hydrazone-type Ligands 12 2.3.4 Thiosemicarbazone/Carbazone-type Ligands 13 2.3.5 Heterocyclic Schiff Bases 14 2.4 Different Bonding Modes of Schiff Bases 14 2.4.1 Monodentate 14 2.4.2 Bidentate 15 2.4.3 Tridentate 15 2.4.4 Tetradentate 16 2.4.5 Pentadentate 17 2.4.6 Hexadentate 17 References 17 3 Different Routes of Synthesis 23 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 3.1 Formation of Schiff Bases 23 3.1.1 Direct Ligand Synthesis 24 3.1.2 Template Synthesis 25 3.1.3 Rearrangement of Heterocycles (Oxazoles, Thiazoles, etc.) 26 References 26 4 Schiff Base Metal Complexes 29 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman References 34 5 Effect of Different Parameters on Schiff Base and their Metal Complex 37 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 5.1 Ionic Charge 37 5.2 Ionic Size 37 5.3 Nature of Central Metal Ions 37 5.4 Nature of the Ligand 37 5.4.1 Basic Character of the Ligand 38 5.4.2 Size and Charge of the Ligand 38 5.4.3 Concentration of Ligand 38 5.4.4 Substitution Effect 38 5.4.5 Chelating Effect 39 5.4.6 Nature of Solvent 39 5.4.7 Crystal Field Effect 39 5.4.8 Thermodynamic and Kinetic Effect 39 References 40 6 Thioether and Chiral Schiff Base 41 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 6.1 Thioether Schiff Base 41 6.2 Chiral Schiff Base 44 References 45 Part II Synthesis 53 7 General Routes of Synthesis 55 Himadri Priya Gogoi, Anmol Singh, and Pranjit Barman 7.1 Introduction 55 7.2 Mechanism of the Synthesis of Schiff Base Ligand 56 7.3 Problems Found in Conventional Method – Hydrolysis of C=NBond 59 References 59 8 Different Route of Synthesis of Schiff Base-Metal Complexes 61 Himadri Priya Gogoi, Anmol Singh, and Pranjit Barman 8.1 Introduction 61 8.2 Different Chemical Routes 61 8.2.1 Preparation of Schiff’s Bases via Aerobic Oxidative Synthesis 61 8.2.2 Synthesis of Schiff Bases via Addition of Organometallic Reagents to Cyanides 61 8.2.3 Reaction of Phenol with Nitriles to Form SB 62 8.2.4 Reaction of Metal Amides to Ketone to Form SB 63 8.2.5 Reaction of Nitroso Compounds with Active Hydrogen Compounds 63 8.2.6 Dehydrogenation of Amines 64 8.2.7 Oxidation of Metal Amines to Form SB 64 8.2.8 Reduction of Carbon–Nitrogen Compounds 65 8.2.9 Synthesis of SB from Ketals 65 8.2.10 SB Synthesis by Using Hydrazoic Acid 66 8.2.11 SB Synthesis by Using Sodium Hypochlorite 66 8.2.12 Preparation of N-metallo Imines 66 8.2.13 Preparation of N-metallo Imines (Metal = B, Al, Si, Sn) 67 8.2.13.1 Preparation of N-boryl and N-aluminum Imines 67 8.2.13.2 Preparation of N-silylimines via 67 8.2.13.3 Preparation of N-tin Imines 68 8.3 Different Methods 68 8.3.1 Classical or Conventional Method 69 8.3.2 Microwave Irradiation Method 70 8.3.3 Water as Solvent Method 71 8.3.4 Grindstone Technique 71 8.3.5 Ultrasonic Method 72 8.3.6 Green Method Using Green Catalyst 73 References 76 9 Synthesis and Mechanism of Schiff Base-Metal Complexes 79 Himadri Priya Gogoi, Anmol Singh, and Pranjit Barman 9.1 Introduction 79 9.2 Synthesis of Schiff Bases Metal Complexes 79 9.2.1 Synthesis of Ligand Followed by Complexation 79 9.2.1.1 One-Step Process or Template Synthesis 80 9.3 Synthesis of Some of the Schiff Base Metal Complexes 83 References 86 10 Synthesis and Mechanism of Chiral and Achiral Schiff Base and Their Metal Complexes 89 Himadri Priya Gogoi, Anmol Singh, and Pranjit Barman 10.1 Introduction 89 10.2 Synthesis of Chiral and Achiral SB Ligand 90 10.3 Synthesis of Chiral SB Metal Complexes 93 10.4 Chiral Schiff Bases of Titanium, Zirconium, and Vanadium 95 10.5 Chiral Schiff Bases of Main Group Metals 96 10.5.1 Manganese and Chromium Schiff Bases 97 10.5.2 Iron and Ruthenium Schiff Base Complexes 98 10.5.3 Cobalt, Nickel, Copper, and Zinc Schiff Base Complexes 98 10.5.4 Lanthanide Metal Schiff Bases 99 10.5.5 Silicon and Tin Metal Schiff Bases 99 References 102 11 Synthesis and Mechanism of Thioether: Schiff Base and Their Metal Complexes 105 Himadri Priya Gogoi, Anmol Singh, and Pranjit Barman 11.1 Introduction 105 11.2 Chemical Synthesis Procedures 106 11.2.1 Procedure for the Synthesis of Thioether-Containing Schiff Base 106 References 111 12 Computational Chemistry 113 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 12.1 Introduction 113 12.2 Application of DFT in the Field of Schiff Base and Their Metal Complexes 115 References 118 Part III Application 119 13 General Applications of Schiff Bases and Their Metal Complexes 121 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman 13.1 Catalyst 121 13.2 Biological and Medicinal Importance 122 13.2.1 Antibacterial Activity 122 13.2.2 Anticancer and Anti-inflammatory Agent 122 13.2.3 Antifungal Activity 123 13.2.4 As a Drug in a Number of Diseases 123 13.3 Coatings 123 13.4 Analytical Chemistry 123 13.5 Dyes 124 13.6 Semi-conducting Materials 124 13.7 Solar System 124 13.8 Photocatalyst 125 13.9 Polymer Chemistry 125 13.10 Agrochemical Industry 125 References 125 14 Application in Pharmacological Field 129 Parnashabari Sarkar, Sourav Sutradhar, and Biswa Nath Ghosh 14.1 Introduction 129 14.2 Antimicrobial Activity 135 14.2.1 Schiff Bases Against Gram-Positive Bacteria 135 14.2.2 Schiff Bases Against Gram-Negative Bacteria 137 14.3 Antifungal Activity of Schiff Bases 138 14.4 Anticancer Activity of Schiff Bases and Their Metal Complexes 139 14.4.1 In Vitro Activity 139 14.4.2 In Vivo Activity 140 14.5 Antidyslipidemic and Antioxidant Activity 141 14.6 Anthelmintic Activity 141 14.7 Antitubercular Activity 142 14.8 Antidepressant Activity 142 14.9 Anticonvulsant Activity 142 14.10 Antioxidant Activity 142 14.11 Antiviral Activity 143 14.12 Anti-inflammatory and Analgesic Activities 143 References 143 15 Application as Catalyst 149 Saravanan Saranya and Seenuvasan Vedachalam 15.1 Introduction 149 15.2 Coupling Reaction 149 15.3 Polymerization Reaction 151 15.4 Oxidation Reaction 152 15.5 Epoxidation Reaction 153 15.6 Ring-Opening Epoxidation Reaction 154 15.7 Cyclopropanation Reaction 155 15.8 Hydrosilylation Reaction 156 15.9 Hydrogenation Reaction 157 15.10 Aldol Reaction 158 15.11 Michael Addition Reaction 159 15.12 Annulation Reaction 160 15.13 Diels–Alder Reaction 161 15.14 Click Reaction 161 15.15 Mannich Reaction 162 15.16 Ene Reaction 163 15.17 Summary 164 References 164 16 Application as Drug-Delivery System 169 Anmol Singh, Himadri Priya Gogoi, and Pranjit Barman References 173 17 Chemosensors/Bioimaging Applications 179 K. Sekar, K. Suganya Devi, T. Dheepa, and P. Srinivasan 17.1 Introduction 179 17.1.1 Chemosensing 179 17.1.1.1 Explosives Sensing 179 17.1.1.2 Oxygen Sensing 180 17.1.1.3 High pH Sensing 180 17.1.1.4 Other Porphyrinoid-based Chemosensors and Chemodosimeters 180 17.1.1.5 Metal Sensing 180 17.2 Chemosensors 181 17.2.1 Fluorescence ON-OFF 184 17.2.1.1 Tiny Molecules Chemosensors 184 17.2.1.2 Supramolecular Chemosensors 184 17.2.1.3 QDs-based Chemosensors 184 17.2.1.4 Fluorescent Nanomaterial-based Chemosensors 185 17.2.2 OFF-ON Chemosensors 185 17.2.2.1 Rhodamine-based Sensors 185 17.2.2.2 Coumarin-based Sensors 186 17.2.2.3 BODIPY-based Sensors 186 17.2.3 Ratiometric Fluorescent Chemosensors 186 17.2.3.1 Pyrene-based Chemosensors 186 17.2.3.2 Fluorophore Hybridization Chemosensors 186 17.2.3.3 Dual-emission Fluorescent Nanoparticles 186 17.2.4 Rhodamine-based Sensors 187 17.2.4.1 Fluorescent Bioimaging of CK in HeLa cells 187 17.2.4.2 Mice Bioimaging Experiments 187 17.2.5 Fluorescent Chemosensor for AcO − Detection 189 17.2.6 CN − and Al 3+ Chemosensor for Bioimaging 191 17.3 Conclusion 192 References 192 18 Application in Industrial Field 195 M. Chakkarapani, M.A. Asha Rani, G. Saravana Ilango, and Pranjit Barman 18.1 Introduction 195 18.2 Current Status in India 198 18.3 Conclusion 199 References 200 Index 203
Pranjit Barman, PhD, is Professor of Chemistry at the National Institute of Technology, Silchar, Assam, India. He has published widely on organometallics and related areas of research. Anmol Singh is a Research Scholar at the National Insitute of Technology, Silchar, Assam, India, studying Schiff bases and organometallics.
