لایب سان

1. Introduction 1 Alaa S. Abd-El-Aziz and Charles E. Carraher Jr. I. Coverage 2 II. General Concepts 3 III. Historical 5 IV. Polymers Containing Bis(Cyclopentadienyl) Metal Complexes 7 A. Polymerization of Olefin-Functionalized Metallocenes 8 B. Alkyne Metathesis Polymerization of Substituted Metallocenes 11 C. Polycondensation of Metallocenes 13 D. Ring-Opening Polymerization 15 E. Coordination of Metals to Cyclopentadienyl Rings 18 F. Introduction of Metallocenes into Preformed Polymers 20 V. Arene-Transition Metal Polymers 21 A. Polymerization of Olefin-Containing Arenes 21 B. Ring-Opening Metathesis Polymerization of Substituted Norbornenes 22 C. Nucleophilic Aromatic Substitution Polymerization of Chloroarene Complexes 23 D. Polycondensation of Arene Complexes 27 E. Coordination of Organometallic Moieties to Arenes 29 F. Supramolecular Assembly of Polymers 30 VI. Polymers with Metal-Coordinated Cyclobutadienes 31 VII. Polymers Containing Metal Carbonyl Complexes 32 VIII. Polymers with Metal-Carbon σ–Bonds 34 A. Transition Metal Polyynes 34 B. Metal-Aryl and Metal-Alkyl Systems 37 IX. Metal–Metal Bonded Systems 38 X. Conclusion 41 XI. References 41 Contents vii Vol-6-Abd-El-Aziz-FM.qxd 9/8/05 12:20 PM Page vii viii Contents 2. Lithographic Applications of Highly Metallized Polyferrocenylsilanes 49 Alison Y. Cheng, Scott B. Clendenning, and Ian Manners I. Introduction 50 II. Polyferrocenylsilanes as Electron Beam Lithography Resists 52 III. Polyferrocenylsilanes as Reactive Ion Etch Resists 53 IV. Polyferrocenylsilanes as UV Photoresists 55 V. Conclusions 56 VI. Acknowledgments 56 VII. References 57 3. Polymers Possessing Reactive Metallacycles in the Mainchain 59 Ikuyoshi Tomita I. Introduction 60 II. Synthesis and Reactions of Organometallic Polymers Possessing Metallacycles in the Mainchain 61 A. Cobaltacyclopentadiene-Containing Polymers 61 B. Conversion of Cobaltacyclopentadiene-Containing Polymers into Polymers Possessing Various Mainchain Structures 63 i. Conversion into Other Organometallic Polymers 63 ii. Conversion into Organic Polymers with Various Functional Groups in the Mainchain 66 C. Synthesis and Reactions of Titanacycle-Containing Polymers 69 i. Polymers Containing Titanacyclopentadiene Unit in the Mainchain 69 ii. Polymers Possessing Other Titanacycle Units 73 III. Summary 74 IV. References 75 4. Mechanistic Aspects of the Photodegradation of Polymers Containing Metal–Metal Bonds Along Their Backbones 77 David R. Tyler I. Introduction 78 II. General Overview of Polymer Photodegradation 79 A. The Auto-Oxidation Mechanism 79 B. Reactions of Hydroperoxide Species That Lead to Backbone Degradation 80 C. Other Photochemical Degradation Mechanisms 82 D. Methods for Intentionally Making Polymers Photodegradable 83 III. Metal–Metal Bond-Containing Polymers 85 A. Synthesis and Characterization 85 B. Synthesis of the Difunctional Dimers 86 C. Synthesis of the Polymers 88 D. Characterization of the Polymers 90 Vol-6-Abd-El-Aziz-FM.qxd 9/8/05 12:20 PM Page viii E. Photochemical Reactions in Solution 91 F. Photochemistry in the Solid State 94 IV. Factors Controlling the Rate of Photochemical Degradation 95 A. Cage Effects 95 B. The Effect of Tensile Stress on Photodegradation 98 i. Theories of Stress-Induced Photodegradation 98 ii. Stress-Induced Changes in φhomolysis; the Plotnikov Hypothesis 99 iii. Stress-Induced Changes in krecombination; the Decreased Radical Recombination Efficiency Hypothesis 100 iv. Stress-Induced Changes in the Rates of Radical Reactions Subsequent to Radical Formation 100 v. The Zhurkov Equation 100 vi. Quantum Yields as a Function of Stress for Polymer 3 101 C. Other Factors Affecting Photochemical Degradation Rates of Polymers 102 i. Absorbed Light Intensity 103 ii. Polymer Morphology 104 iii. Oxygen Diffusion 105 iv. Chromophore Concentration 106 V. Acknowledgments 106 VI. References 106 5. Zirconocene and Hafnocene-Containing Macromolecules 111 Charles E. Carraher Jr. I. General 112 II. Introduction 113 III. Inorganic Supported Zirconocene and Hafnocene Catalysts 116 IV. Other Supports 119 V. Condensation Reactions with Monomeric Lewis Bases 121 VI. Zirconocene and Hafnocene Reactions with Already Existing Polymers 137 VII. Miscellaneous 139 VIII. Summary 143 IX. References 143 6. Compositional and Structural Irregularities of Macromolecular Metal Complexes 147 Anatolii D. Pomogailo, Gulzhian I. Dzhardimalieva I. Introduction 148 II. Basic Transformations of Macroligands in Binding MXn 150 A. Conformational Changes in Polymer Chains 150 B. Macroligand Structuring Processes 152 Contents ix Vol-6-Abd-El-Aziz-FM.qxd 9/8/05 12:20 PM Page ix x Contents C. Macroligand Decomposition in MXn–Polymer Systems 155 D. Changes in Origin of Functional Groups of Polymers in Their Reactions with MXn 159 III. Transformation of Transition Metal Compounds in Reactions with Polymers 161 A. Oxidation–Reduction Conversion of Transition Metals 161 B. Monomerization of Transition Metal Dimer Complexes in Reactions with Polymers 162 C. Composite Inhomogeneity of Macromolecular Complexes 164 IV. Problem of Topochemistry of Macromolecular Complexes 166 A. Topochemistry of Polymer Macroligand Functional Layers 166 B. Topochemistry of Diamagnetic Complexes That Are Fixed to the Polymers 167 C. Topochemistry of Polymer-Bonded Paramagnetic Complexes 168 D. The Main Data on MMC Topochemistry 172 V. Problems of Unit Variability in Metal-Containing Polymers Obtained by Copolymerization of Metal-Containing Monomers 172 A. Unit Variability Due to Elimination of a Metal-Containing Group During Polymerization 175 B. Unit Variability Due to Different Valence States of the Transition Metal Ions 177 C. Unit Variability Due to the Presence of Stable Metal Isotopes 179 D. Anomalies in Metallopolymeric Chains Caused by the Diversity of Chemical Binding of a Metal to Polymerizable Ligands 180 E. Unit Variability Due to Qualitatively and Quantitatively Different Ligand Environments of the Metal 183 F. Extra-Coordination as a Spatial and Electronic Anomaly of the Polyhedron 186 G. Exchange Interactions Between Metal Ions Incorporated in the Chain 188 H. Change in the Nuclearity of Metal Sites as a Type of Unit Variability 190 I. Stereoregularity of Metallopolymeric Chains 192 J. Unit Variability Due to Chirality in Pendant Groups 194 K. Unsaturation and Structurization of Metallopolymers 196 L. Cyclization During Polymerization 197 VI. Some Practical Applications of Unit Variability of Metal-Containing Polymers 198 VII. Acknowledgments 202 VIII. References 202 Index 209

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