Macromolecules Containing Metal and

This series provides a useful, applications-oriented forum for the next generation of macromolecules and materials. The sixth volume in this series provides useful descriptions of the transition metals and their applications, edited by high-quality team of macromolecular experts from around the world.

Dr. Alaa Abd-El-Aziz is Professor of Chemistry and the Associate Vice-President of Research & Graduate Studies at the University of Winnipeg.

Dr. Charles Carraher is Professor of Chemistry at Florida Atlantic University and Associate Director of the Florida Center for Environmental Studies.

Dr. Charles Pittman has a B.S. in Chemical Engineering from Lafayette College and a Ph.D. in Organic Chemistry from Pennsylvania State University. He completed postdoctoral studies with G. A. Olah, and served on active duty at the U.S. Army University of Alabama. He was appointed Full Professor in 1975 and University Research Professor in 1977. Dr. Pittman came to Mississippi State in 1983 as Professor of Industrial Chemistry and Catalysis. He is also Research Director of the University/Industry Chemical Research Center.

Martin Zeldin is Visiting Senior Research Scholar at the University of Richmond in Virginia. He received his Ph.D. in inorganic chemistry in 1968 from Pennsylvania State University.

Preface

xi

Series Preface

xiii

Introduction

1

(48)

Alaa S. Abd-El-Aziz

Charles E. Carraher Jr.

Coverage

2

(1)

General Concepts

3

(2)

Historical

5

(2)

Polymers Containing Bis(Cyclopentadienyl) Metal Complexes

7

(14)

Polymerization of Olefin-Functionalized Metallocenes

8

(3)

Alkyne Metathesis Polymerization of Substituted Metallocenes

11

(2)

Polycondensation of Metallocenes

13

(2)

Ring-Opening Polymerization

15

(3)

Coordination of Metals to Cyclopentadienyl Rings

18

(2)

Introduction of Metallocenes into Preformed Polymers

20

(1)

Arene-Transition Metal Polymers

21

(10)

Polymerization of Olefin-Containing Arenes

21

(1)

Ring-Opening Metathesis Polymerization of Substituted Norbornenes

22

(1)

Nucleophilic Aromatic Substitution Polymerization of Chloroarene Complexes

23

(4)

Polycondensation of Arene Complexes

27

(2)

Coordination of Organometallic Moieties to Arenes

29

(1)

Supramolecular Assembly of Polymers

30

(1)

Polymers with Metal-Coordinated Cyclobutadienes

31

(1)

Polymers Containing Metal Carbonyl Complexes

32

(2)

Polymers with Metal-Carbon σ--Bonds

34

(4)

Transition Metal Polyynes

34

(3)

Metal-Aryl and Metal-Alkyl Systems

37

(1)

Metal--Metal Bonded Systems

38

(3)

Conclusion

41

(1)

References

41

(8)

Lithographic Applications of Highly Metallized Polyferrocenylsilanes

49

(10)

Alison Y. Cheng

Scott B. Clendenning

Ian Manners

Introduction

50

(2)

Polyferrocenylsilanes as Electron Beam Lithography Resists

52

(1)

Polyferrocenylsilanes as Reactive Ion Etch Resists

53

(2)

Polyferrocenylsilanes as UV Photoresists

55

(1)

Conclusions

56

(1)

Acknowledgments

56

(1)

References

57

(2)

Polymers Possessing Reactive Metallacycles in the Mainchain

59

(18)

Ikuyoshi Tomita

Introduction

60

(1)

Synthesis and Reactions of Organometallic Polymers Possessing Metallacycles in the Mainchain

61

(13)

Cobaltacyclopentadiene-Containing Polymers

61

(2)

Conversion of Cobaltacyclopentadiene-Containing Polymers into Polymers Possessing Various Mainchain Structures

63

(1)

Conversion into Other Organometallic Polymers

63

(3)

Conversion into Organic Polymers with Various Functional Groups in the Mainchain

66

(3)

Synthesis and Reactions of Titanacycle-Containing Polymers

69

(1)

Polymers Containing Titanacyclopentadiene Unit in the Mainchain

69

(4)

Polymers Possessing Other Titanacycle Units

73

(1)

Summary

74

(1)

References

75

(2)

Mechanistic Aspects of the Photodegradation of Polymers Containing Metal--Metal Bonds Along Their Backbones

77

(34)

David R. Tyler

Introduction

78

(1)

General Overview of Polymer Photodegradation

79

(6)

The Auto-Oxidation Mechanism

79

(1)

Reactions of Hydroperoxide Species That Lead to Backbone Degradation

80

(2)

Other Photochemical Degradation Mechanisms

82

(1)

Methods for Intentionally Making Polymers Photodegradable

83

(2)

Metal--Metal Bond-Containing Polymers

85

(10)

Synthesis and Characterization

85

(1)

Synthesis of the Difunctional Dimers

86

(2)

Synthesis of the Polymers

88

(2)

Characterization of the Polymers

90

(1)

Photochemical Reactions in Solution

91

(3)

Photochemistry in the Solid State

94

(1)

Factors Controlling the Rate of Photochemical Degradation

95

(11)

Cage Effects

95

(3)

The Effect of Tensile Stress on Photodegradation

98

(1)

Theories of Stress-Induced Photodegradation

98

(1)

Stress-Induced Changes in φhomolysis; the Plotnikov Hypothesis

99

(1)

Stress-Induced Changes in krecombination; the Decreased Radical Recombination Efficiency Hypothesis

100

(1)

Stress-Induced Changes in the Rates of Radical Reactions Subsequent to Radical Formation

100

(1)

The Zhurkov Equation

100

(1)

Quantum Yields as a Function of Stress for Polymer 3

101

(1)

Other Factors Affecting Photochemical Degradation Rates of Polymers

102

(1)

Absorbed Light Intensity

103

(1)

Polymer Morphology

104

(1)

Oxygen Diffusion

105

(1)

Chromophore Concentration

106

(1)

Acknowledgments

106

(1)

References

106

(5)

Zirconocene and Hafnocene-Containing Macromolecules

111

(36)

Charles E. Carraher Jr.

General

112

(1)

Introduction

113

(3)

Inorganic Supported Zirconocene and Hafnocene Catalysts

116

(3)

Other Supports

119

(2)

Condensation Reactions with Monomeric Lewis Bases

121

(16)

Zirconocene and Hafnocene Reactions with Already Existing Polymers

137

(2)

Miscellaneous

139

(4)

Summary

143

(1)

References

143

(4)

Compositional and Structural Irregularities of Macromolecular Metal Complexes

147

(62)

Anatolii D. Pomogailo

Gulzhian I. Dzhardimalieva

Introduction

148

(2)

Basic Transformations of Macroligands in Binding MXn

150

(11)

Conformational Changes in Polymer Chains

150

(2)

Macroligand Structuring Processes

152

(3)

Macroligand Decomposition in MXn--Polymer Systems

155

(4)

Changes in Origin of Functional Groups of Polymers in Their Reactions with MXn

159

(2)

Transformation of Transition Metal Compounds in Reactions with Polymers

161

(5)

Oxidation--Reduction Conversion of Transition Metals

161

(1)

Monomerization of Transition Metal Dimer Complexes in Reactions with Polymers

162

(2)

Composite Inhomogeneity of Macromolecular Complexes

164

(2)

Problem of Topochemistry of Macromolecular Complexes

166

(6)

Topochemistry of Polymer Macroligand Functional Layers

166

(1)

Topochemistry of Diamagnetic Complexes That Are Fixed to the Polymers

167

(1)

Topochemistry of Polymer-Bonded Paramagnetic Complexes

168

(4)

The Main Data on MMC Topochemistry

172

(1)

Problems of Unit Variability in Metal-Containing Polymers Obtained by Copolymerization of Metal-Containing Monomers

172

(26)

Unit Variability Due to Elimination of a Metal-Containing Group During Polymerization

175

(2)

Unit Variability Due to Different Valence States of the Transition Metal Ions

177

(2)

Unit Variability Due to the Presence of Stable Metal Isotopes

179

(1)

Anomalies in Metallopolymeric Chains Caused by the Diversity of Chemical Binding of a Metal to Polymerizable Ligands

180

(3)

Unit Variability Due to Qualitatively and Quantitatively Different Ligand Environments of the Metal

183

(3)

Extra-Coordination as a Spatial and Electronic Anomaly of the Polyhedron

186

(2)

Exchange Interactions Between Metal Ions Incorporated in the Chain

188

(2)

Change in the Nuclearity of Metal Sites as a Type of Unit Variability

190

(2)

Stereoregularity of Metallopolymeric Chains

192

(2)

Unit Variability Due to Chirality in Pendant Groups

194

(2)

Unsaturation and Structurization of Metallopolymers

196

(1)

Cyclization During Polymerization

197

(1)

Some Practical Applications of Unit Variability of Metal-Containing Polymers

198

(4)

Acknowledgments

202

(1)

References

202

(7)

Index

209

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Macromolecules Containing Metal and Metal-Like Elements Vol. 6 : Transition Metal-Containing Polymers

Summary

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Table of Contents

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Macromolecules Containing Metal and Metal-Like Elements Vol. 6 : Transition Metal-Containing Polymers

Summary

Author Biography

Table of Contents

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