Macromolecules Containing Metal and Metal-Like Elements, Transition Metals, Part II, Vol. 6 Book

Preface     xi
Series Preface     xiii
Introduction   Alaa S. Abd-El-Aziz   Charles E. Carraher Jr.     1
Coverage     2
General Concepts     3
Historical     5
Polymers Containing Bis(Cyclopentadienyl) Metal Complexes     7
Polymerization of Olefin-Functionalized Metallocenes     8
Alkyne Metathesis Polymerization of Substituted Metallocenes     11
Polycondensation of Metallocenes     13
Ring-Opening Polymerization     15
Coordination of Metals to Cyclopentadienyl Rings     18
Introduction of Metallocenes into Preformed Polymers     20
Arene-Transition Metal Polymers     21
Polymerization of Olefin-Containing Arenes     21
Ring-Opening Metathesis Polymerization of Substituted Norbornenes     22
Nucleophilic Aromatic Substitution Polymerization of Chloroarene Complexes     23
Polycondensation of Arene Complexes     27
Coordination of Organometallic Moieties to Arenes     29
Supramolecular Assembly of Polymers     30
Polymers with Metal-Coordinated Cyclobutadienes     31
Polymers Containing Metal Carbonyl Complexes     32
Polymers with Metal-Carbon[sigma]-Bonds     34
Transition Metal Polyynes     34
Metal-Aryl and Metal-Alkyl Systems     37
Metal-Metal Bonded Systems     38
Conclusion     41
References     41
Lithographic Applications of Highly Metallized Polyferrocenylsilanes   Alison Y. Cheng   Scott B. Clendenning   Ian Manners     49
Introduction     50
Polyferrocenylsilanes as Electron Beam Lithography Resists     52
Polyferrocenylsilanes as Reactive Ion Etch Resists     53
Polyferrocenylsilanes as UV Photoresists     55
Conclusions     56
Acknowledgments     56
References     57
Polymers Possessing Reactive Metallacycles in the Mainchain   Ikuyoshi Tomita     59
Introduction     60
Synthesis and Reactions of Organometallic Polymers Possessing Metallacycles in the Mainchain     61
Cobaltacyclopentadiene-Containing Polymers     61
Conversion of Cobaltacyclopentadiene-Containing Polymers into Polymers Possessing Various Mainchain Structures     63
Conversion into Other Organometallic Polymers     63
Conversion into Organic Polymers with Various Functional Groups in the Mainchain     66
Synthesis and Reactions of Titanacycle-Containing Polymers     69
Polymers Containing Titanacyclopentadiene Unit in the Mainchain     69
Polymers Possessing Other Titanacycle Units     73
Summary     74
References     75
Mechanistic Aspects of the Photodegradation of Polymers Containing Metal-Metal Bonds Along Their Backbones   David R. Tyler     77
Introduction     78
General Overview of Polymer Photodegradation     79
The Auto-Oxidation Mechanism     79
Reactions of Hydroperoxide Species That Lead to Backbone Degradation     80
Other Photochemical Degradation Mechanisms     82
Methods for Intentionally Making Polymers Photodegradable     83
Metal-Metal Bond-Containing Polymers     85
Synthesis and Characterization     85
Synthesis of the Difunctional Dimers     86
Synthesis of the Polymers     88
Characterization of the Polymers     90
Photochemical Reactions in Solution     91
Photochemistry in the Solid State     94
Factors Controlling the Rate of Photochemical Degradation     95
Cage Effects     95
The Effect of Tensile Stress on Photodegradation     98
Theories of Stress-Induced Photodegradation     98
Stress-Induced Changes in [Phi subscript homolysis]; the Plotnikov Hypothesis     99
Stress-Induced Changes in k[subscript recombination]; the Decreased Radical Recombination Efficiency Hypothesis     100
Stress-Induced Changes in the Rates of Radical Reactions Subsequent to Radical Formation     100
The Zhurkov Equation     100
Quantum Yields as a Function of Stress for Polymer 3     101
Other Factors Affecting Photochemical Degradation Rates of Polymers     102
Absorbed Light Intensity     103
Polymer Morphology     104
Oxygen Diffusion     105
Chromophore Concentration     106
Acknowledgments     106
References     106
Zirconocene and Hafnocene-Containing Macromolecules   Charles E. Carraher Jr.     111
General     112
Introduction     113
Inorganic Supported Zirconocene and Hafnocene Catalysts     116
Other Supports     119
Condensation Reactions with Monomeric Lewis Bases     121
Zirconocene and Hafnocene Reactions with Already Existing Polymers     137
Miscellaneous     139
Summary     143
References     143
Compositional and Structural Irregularities of Macromolecular Metal Complexes   Anatolii D. Pomogailo   Gulzhian I. Dzhardimalieva     147
Introduction     148
Basic Transformations of Macroligands in Binding MX[subscript n]     150
Conformational Changes in Polymer Chains     150
Macroligand Structuring Processes     152
Macroligand Decomposition in MX[subscript n]-Polymer Systems     155
Changes in Origin of Functional Groups of Polymers in Their Reactions with MX[subscript n]     159
Transformation of Transition Metal Compounds in Reactions with Polymers     161
Oxidation-Reduction Conversion of Transition Metals     161
Monomerization of Transition Metal Dimer Complexes in Reactions with Polymers     162
Composite Inhomogeneity of Macromolecular Complexes     164
Problem of Topochemistry of Macromolecular Complexes     166
Topochemistry of Polymer Macroligand Functional Layers     166
Topochemistry of Diamagnetic Complexes That Are Fixed to the Polymers     167
Topochemistry of Polymer-Bonded Paramagnetic Complexes     168
The Main Data on MMC Topochemistry     172
Problems of Unit Variability in Metal-Containing Polymers Obtained by Copolymerization of Metal-Containing Monomers     172
Unit Variability Due to Elimination of a Metal-Containing Group During Polymerization     175
Unit Variability Due to Different Valence States of the Transition Metal Ions     177
Unit Variability Due to the Presence of Stable Metal Isotopes     179
Anomalies in Metallopolymeric Chains Caused by the Diversity of Chemical Binding of a Metal to Polymerizable Ligands     180
Unit Variability Due to Qualitatively and Quantitatively Different Ligand Environments of the Metal     183
Extra-Coordination as a Spatial and Electronic Anomaly of the Polyhedron     186
Exchange Interactions Between Metal Ions Incorporated in the Chain     188
Change in the Nuclearity of Metal Sites as a Type of Unit Variability     190
Stereoregularity of Metallopolymeric Chains     192
Unit Variability Due to Chirality in Pendant Groups     194
Unsaturation and Structurization of Metallopolymers     196
Cyclization During Polymerization     197
Some Practical Applications of Unit Variability of Metal-Containing Polymers     198
Acknowledgments     202
References     202
Index     209