Bonding in cluster compounds

The study of cluster compounds is an active area of current research. The scope is widening and systematic methods of synthesis beginning to appear based, for example, on the isolobal principle first mentioned in Chapter 10 and which will be met again lat

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Physica Inorganic Chemistry A Coordination Chemistry Approach

S. F. A. KETTLE Professorial Fellow, University of East Anglia, and Adjunct Professor, Royal Military College, Kingston, Ontario

Springer-Verlag Berlin Heidelberg GmbH

In memory of Doreen, 1929-1994

British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library. ISBN 978-3-662-25191-1 (eBook) ISBN 978-0-7167-4514-3 DOI 10.1007/978-3-662-25191-1 Library of Congress Cataloging-in-Publication Data Kettle, S. F. A. (Sidney Francis Alan) Physical inorganic chemistry: a coordination chemistry approach I Sidney F. A. Kettle p. em. Includes bibliographical references and index 1. Physical inorganic chemistry 2. Coordination compounds. I. Title.

QD475.K46 1996

541.2'242-dc20

95---44747

Copyright© 1996 S. F. A. Kettle Originally published by Spektrum Academic Publishers in 1996 No part of this publication may be reproduced by any mechanical, photographic, or electronic process, or in the form of phonographic recording, nor may it be stored in a retrieval system, transmitted, or otherwise copied for public or private use without written permission of the publisher. Set by KEYWORD Publishing Services, London

CIP

Contents Foreword

xiii

Preface

'IN

3.3 What determines coordination number and geometry? 42 3.4 Isomerism in coordination compounds

43

1

3.4.1 Conformation isomerism

43

Introduction

3.4.2 Geometrical isomerism

44

1

3.4.3 Coordination position isQmerism

44

3.4.4 Coordination isomerism

44

7

3.4.5 Ionization isomerism

45

7

3.4.6 Hydrate isomerism

45

3.4.7 Linkage isomerism

45

3.4.8 Polymerization isomerism

45

3.4.9 Ligand isomerism

46

3.4.10 Optical isomerism

46

3.4.11 Structural and fluxional isomerism

47

3.4.12 Spin isomerism

48

2 Typical ligands, typical complexes 2.1 Classical ligands, classical complexes 2.2 Novel ligands, novel complexes 2.3 Some final comments

10 21

3 Nomenclature, geometrical structure and isomerism of coordination compounds

24

3.1 Nomenclature

24

3.2 Coordination numbers

31

3.2.1 Complexes with coordination numbers

one, two or three

32

3.2.2 Complexes with coordination number

four

33

3.2.3 Complexes with coordination number

five

35

3.2.4 Complexes with coordination number

six

38

3.2.5 Complexes with coordination number

seven

38

3.2.6 Complexes with coordination number

eight

39

3.2.7 Complexes with coordination number

nine

41

3.2.8 Complexes of higher coordination

number

4 Preparation of coordination compounds

51

4.1 Introduction

51

4.2 Preparative methods

52

4.2.1 Simple addition reactions

52

4.2.2 Substitution reactions

54

4.2.3 Oxidation-reduction reactions

58

4.2.4 Thermal dissociation reactions

61

4.2.5 Preparations in the absence of oxygen

62

4.2.6 Reactions of coordinated ligands

65

4.2.7 The trans effect

68

4.2.8 Other methods of preparing

41

coordination compounds

69

viii

1

Contents

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