All rights reserved. Wiley also publishes its books in a variety of electronic formats. Library of Congress Cataloging-in-Publication Data Lawrance, Geoffrey A. Introduction to coordination chemistry / Geoffrey A. Lawrance. If professional advice or other expert assistance – why not find out more – is required, the services of a competent professional should be sought. The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. The publisher is not associated with any product or vendor mentioned in this book. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. The advice and strategies contained herein may not be suitable for every situation. Designations used by companies to distinguish their products are often claimed as trademarks. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. Some content that appears in print may not be available in electronic books. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. This work is sold with the understanding that the publisher is not engaged in rendering professional services. Printed and bound in Great Britain by CPI Antony Rowe, Chippenham, Wiltshire P1: OTE/OTE/SPH P2: OTE FM JWBK420-Lawrance November 16, 2009 8:45 Printer: Yet to Come Contents Preface . Neither the publisher nor the author shall be liable for any damages arising herefrom. Includes bibliographical references and index. It is sold on the understanding that the publisher is not engaged in rendering professional services. No warranty may be created or extended by any promotional statements for this work.

Preamble . . . 17 2.1.4 Do I Look Big on That? 26 2.2.2 Amines Ain’t Ammines – Ligand Families . 31 2.3.3 Many-Armed Monsters – Introducing Ligand Shape . 12 1.4 The Road Ahead . 15 2.1.1 What Makes a Ligand? 1 1.2 A Who’s Who of Metal Ions . 7 1.3 Metals in Molecules . 1 1.1 Key Concepts in Coordination Chemistry . Chelate Ring Size . 1 The Central Atom . 15 2.1.2 Making Attachments – Coordination . 29 2.3.2 More Teeth, Stronger Bite – Polydentates . 23 2.1.6 Ligands with More Bite – Denticity . 27 2.2.3 Meeting More Metals – Bridging Ligands . 4 1.2.1 Commoners and ‘Uncommoners’ . 32 2.4 Polynucleating Species – Molecular Bigamists . 10 1.3.2 Metals in Contrived Environments . 27 2.3 Greed is Good – Polydentate Ligands . 22 2.1.5 Different Tribes – Donor Group Variation . 26 2.2.1 Basic Binders . 13 Concept Keys . 11 1.3.3 Natural or Made-to-Measure Complexes . 5 1.2.2 Redefining Commoners . 14 2 Ligands . 9 1.3.1 Metals in the Natural World . 14 Further Reading . 29 2.3.1 The Simple Chelate . 15 2.1 Membership: Being a Ligand . 16 2.1.3 Putting the Bite on Metals – Chelation . 24 2.2 Monodentate Ligands – The Simple Type .

75 3.5.1 Selectivity – Of all the Molecules in all the World, Why This One?

33 2.4.1 When One is Not Enough . 42 3.2.1 The Coordinate Bond . 38 Further Reading . 36 Concept Keys . 42 3.2.2 The Foundation of Coordination Chemistry . 86 4.2.2 Two Coordination (ML2) . 75 3.5.1 Selectivity – Of all the Molecules in all the World, Why This One? 75 3.5.2 Preferences – Do You Like What I Like? 113 4.5 Sophisticated Shapes . 101 4.3.2 Moulding a Relationship – Ligand Influences . 33 2.4.2 Vive la Difference – Mixed-metal Complexation . 101 4.3.1 Metallic Genetics – Metal Ion Influences . 41 3.1 The Central Metal Ion . 96 4.2.7 Higher Coordination Numbers (ML7 to ML9) . 109 4.4.4 What’s Best? 81 Further Reading . 73 3.5 Making Choices . 41 3.2 Metal-Ligand Marriage . 34 2.4.3 Supersized – Binding to Macromolecules . 89 4.2.5 Five Coordination (ML5) . 86 4.2.1 One Coordination (ML) . 53 3.3.2 A Covalent Bonding Model – Embracing Molecular Orbital Theory . 106 4.4.2 Constitutional (Structural) Isomerism . 57 3.3.3 Ligand Field Theory – Making Compromises . 88 4.2.4 Four Coordination (ML4) . 115 4.5.1 Compounds of Polydentate Ligands . 83 4.2 Forms of Complex Life – Coordination Number and Shape . 98 4.3 Influencing Shape . 83 4.1 Getting in Shape . 49 3.3.1 An Ionic Bonding Model – Introducing Crystal Field Theory . 77 3.6 Complexation Consequences . 87 4.2.3 Three Coordination (ML3) . 105 4.4.1 Introducing Stereoisomers . 62 3.3.4 Bonding Models Extended . 105 4.4 Isomerism – Real 3D Effects . 80 Concept Keys . 45 3.3 Holding On – The Nature of Bonding in Metal Complexes . 106 4.4.3 Stereoisomerism: in Place – Positional Isomers; in Space – Optical Isomers . 63 3.4 Coupling – Polymetallic Complexes . 75 3.5.3 Complex Lifetimes – Together, Forever? 42 3.2.3 Complex Shape – Not Just Any Which Way . 93 4.2.6 Six Coordination (ML6) . 103 4.3.3 Chameleon Complexes . 36 2.5 A Separate Race – Organometallic Species . Isomer Preferences . . 39 P1: OTE/OTE/SPH P2: OTE FM JWBK420-Lawrance November 16, 2009 8:45 Printer: Yet to Come vi Contents 3 Complexes . 82 4 Shape .

Sterling Silver Spoon Rings

116 4.5.2 Encapsulation Compounds . 160 5.3.4 A New Suit – Ligand-centred Reactions . 216 7.3.2 Pretty in Red? 124 P1: OTE/OTE/SPH P2: OTE FM JWBK420-Lawrance November 16, 2009 8:45 Printer: Yet to Come Contents vii 5 Stability . 146 5.3.1 A New Partner – Substitution . 121 4.6 Defining Shape . Colour and the Spectrochemical Series . 194 6.5.1 Metal-directed Reactions . 178 6.3 Reactions Involving the Coordination Shell . 194 6.5.2 Reactions of Coordinated Ligands . 173 6.1 Molecular Creation – Ways to Make Complexes . 123 Concept Keys . 184 6.3.3 Substitution Reactions without using a Solvent . 138 5.1.4 Undergoing Change – Kinetic Stability . 214 7.3.1 Peak Performance – Illustrating Selected Physical Methods . 173 6.2.1 s Block: Alkali and Alkaline Earth Metals . 174 6.2.3 d Block: Transition Metals . 179 6.3.2 Substitution Reactions in Nonaqueous Solvents . 190 6.4 Reactions Involving the Metal Oxidation State . 179 6.3.1 Ligand Substitution Reactions in Aqueous Solution . 127 5.1.3 Overall Stability Constants . 170 Further Reading . 147 5.3.2 A New Body – Stereochemical Change . 209 7.1 Finding Ways to Make Complexes Talk – Investigative Methods . 143 5.2.1 Thermodynamic and Kinetic Stability . 197 6.6 Organometallic Synthesis . 186 6.3.4 Chiral Complexes . 176 6.2.5 Beyond Natural Elements . 169 Concept Keys . 145 5.3 Reactions . 123 Further Reading . 173 6.2.2 p Block: Main Group Metals . 189 6.3.5 Catalysed Reactions . 141 5.2 Complexation – Will It Last? 144 5.2.3 Lability and Inertness in Octahedral Complexes . 125 5.1 The Makings of a Stable Relationship . 209 7.2 Getting Physical – Methods and Outcomes . 206 Further Reading . 170 6 Synthesis . 125 5.1.1 Bedded Down – Thermodynamic Stability . 143 5.2.2 Kinetic Rate Constants . 207 7 Properties . 155 5.3.3 A New Face – Oxidation-Reduction . 210 7.3 Probing the Life of Complexes – Using Physical Methods . 203 Concept Keys . 190 6.5 Reactions Involving Coordinated Ligands . 125 5.1.2 Factors Influencing Stability of Metal Complexes . 175 6.2.4 f Block: Inner Transition Metals (Lanthanoids and Actinoids) . 117 4.5.3 Host-Guest Molecular Assemblies . 173 6.2 Core Metal Chemistry – Periodic Table Influences .