Organosilanes in radical chemistry 2004 - Chatgilialoglu.pdf - Silicon related - ziolek6661

Organosilanes in

Radical Chemistry

Chryssostomos Chatgilialoglu

Consiglio Nazionale delle Ricerche,

Bologna, Italy

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Library of Congress Cataloging-in-Publication Data

Chatgilialoglu, Chryssostomos.

Organosilanes in radical chemistry/Chryssostomos Chatgilialoglu.

p. cm.

Includes bibliographical references and index.

ISBN 0-471-49870-X (cloth : alk. paper)

1. Organosilicon compounds. 2. Free radicals (Chemistry) I. Title.

QD305. S54C43 2004

547 0 .08–dc22

2003016573

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 0 471 49870 X

Typeset in 10/12 pt Times by Kolam Information Services Pvt Ltd, Pondicherry, India.

Printed and bound in Great Britain by TJ International, Padstow, Cornwall

This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which

at least two trees are planted for each one used for paper production.

DEDICATION

To my parents XrZstoB and PZnelopZ

CONTENTS

Preface x

Acknowledgements xii

1 Formation and Structures of Silyl Radicals 1

1.1 Methods of Generation of Silyl Radicals 1

1.2 Structural Properties of Silyl Radicals 4

1.2.1 Chemical Studies 4

1.2.2 Electron Paramagnetic Resonance (EPR) Spectra 6

1.2.3 Crystal Structures 11

1.2.4 UV–Visible Spectra 13

1.2.5 Theoretical Studies 14

1.3 References 16

2 Thermochemistry 19

2.1 General Considerations 19

2.2 Bond Dissociation Enthalpies 20

2.2.1 Radical Kinetics 20

2.2.2 Photoacoustic Calorimetry 22

2.2.3 Theoretical Data 23

2.2.4 Derived Bond Dissociation Energies 24

2.3 Ion Thermochemistry 25

2.3.1 Negative-ion Cycles 25

2.3.2 Hydride-affinity Cycles 27

2.4 References 28

3 Hydrogen Donor Abilities of Silicon Hydrides 31

3.1 Carbon-centred Radicals 32

3.1.1 Primary Alkyl Radicals and Free-Radical ClockMethodology 32

3.1.2 Other Types of Carbon-centred Radicals 36

3.2 Nitrogen-centred Radicals 38

3.3 Oxygen-centred Radicals 39

3.3.1 Alkoxyl Radicals 39

3.3.2 Peroxyl Radicals 41

3.3.3 Aryloxyl and Aroyloxyl Radicals 41

3.4 Sulfur-centred Radicals 42

3.5 Ketone Triplets 43

viii

Contents

3.6 Hydrogen Atom: An Example of Gas-phase Kinetics 44

3.7 Theoretical Approaches 45

3.8 References 46

4 Reducing Agents 49

4.1 General Aspects of Radical Chain Reactions 49

4.1.1 Radical–Radical Reactions 51

4.2 Radical Initiators 52

4.3 Tris(trimethylsilyl)silane 53

4.3.1 Dehalogenations 55

4.3.2 Reductive Removal of Chalcogen Groups (RS and RSe) 59

4.3.3 Deoxygenation of Alcohols (Barton–McCombie Reaction) 62

4.3.4 Miscellaneous Reactions 66

4.3.5 Appendix 69

4.4 Other Silicon Hydrides 70

4.4.1 Trialkylsilanes 70

4.4.2 Phenyl Substituted Silicon Hydrides 73

4.4.3 Silyl Substituted Silicon Hydrides 76

4.4.4 Alkylthio Substituted Silicon Hydrides 78

4.5 Silicon Hydride/Thiol Mixture 79

4.6 Silanethiols 80

4.7 Silylated Cyclohexadienes 80

4.8 References 82

5 Addition to Unsaturated Bonds 87

5.1 Carbon–Carbon Double Bonds 88

5.1.1 Formation of Silyl Radical Adducts 88

5.1.2 Hydrosilylation of Alkenes 92

5.2 Carbon–Carbon Triple Bonds 97

5.2.1 Formation of Silyl Radical Adducts 97

5.2.2 Hydrosilylation of Alkynes 98

5.3 Carbon–Oxygen Double Bonds 100

5.3.1 Formation of Silyl Radical Adducts 100

5.3.2 Hydrosilylation of Carbonyl Groups 102

5.3.3 Radical Brook Rearrangement 106

5.4 Other Carbon–Heteroatom Multiple Bonds 108

5.5 Cumulenes and Hetero-Cumulenes 110

5.6 Heteroatom–Heteroatom Multiple Bonds 111

5.7 References 115

6 Unimolecular Reactions 119

6.1 Cyclization Reactions of Silyl Radicals 119

6.1.1 Five-membered Ring Expansion 126

6.2 Aryl Migration 129

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