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Macromolecules Containing Metal and Metal-Like Elements, Volume 6: Transition Metal-Containing Polymers

Macromolecules Containing Metal and Metal-Like Elements, Volume 6: Transition Metal-Containing Polymers




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.

Series Preface.

1. Introduction (Alaa S. Abd-El-Aziz and Charles E. Carraher Jr.).

I. Coverage.

II. General Concepts.

III. Historical.

IV. Polymers Containing Bis(Cyclopentadienyl) Metal Complexes.

A. Polymerization of Olefin-Functionalized Metallocenes.

B. Alkyne Metathesis Polymerization of Substituted Metallocenes.

C. Polycondensation of Metallocenes.

D. Ring-Opening Polymerization.

E. Coordination of Metals to Cyclopentadienyl Rings.

F. Introduction of Metallocenes into Preformed Polymers.

V. Arene-Transition Metal Polymers.

A. Polymerization of Olefin-Containing Arenes.

B. Ring-Opening Metathesis Polymerization of Substituted Norbornenes.

C. Nucleophilic Aromatic Substitution Polymerization of Chloroarene Complexes.

D. Polycondensation of Arene Complexes.

E. Coordination of Organometallic Moieties to Arenes.

F. Supramolecular Assembly of Polymers.

VI. Polymers with Metal-Coordinated Cyclobutadienes.

VII. Polymers Containing Metal Carbonyl Complexes.

VIII. Polymers with Metal-Carbon σ–Bonds.

A. Transition Metal Polyynes.

B. Metal-Aryl and Metal-Alkyl Systems.

IX. Metal–Metal Bonded Systems.

X. Conclusion.

XI. References.

2. Lithographic Applications of Highly Metallized Polyferrocenylsilanes (Alison Y. Cheng, Scott B. Clendenning, and Ian Manners).

I. Introduction.

II. Polyferrocenylsilanes as Electron Beam Lithography Resists.

III. Polyferrocenylsilanes as Reactive Ion Etch Resists.

IV. Polyferrocenylsilanes as UV Photoresists.

V. Conclusions.

VI. Acknowledgments.

VII. References.

3. Polymers Possessing Reactive Metallacycles in the Mainchain (Ikuyoshi Tomita).

I. Introduction.

II. Synthesis and Reactions of Organometallic Polymers Possessing Metallacycles in the Mainchain.

A. Cobaltacyclopentadiene-Containing Polymers.

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

i. Conversion into Other Organometallic Polymers.

ii. Conversion into Organic Polymers with Various Functional Groups in the Mainchain.

C. Synthesis and Reactions of Titanacycle-Containing Polymers.

i. Polymers Containing Titanacyclopentadiene Unit in the Mainchain.

ii. Polymers Possessing Other Titanacycle Units.

III. Summary.

IV. References.

4. Mechanistic Aspects of the Photodegradation of Polymers Containing Metal–Metal Bonds Along Their Backbones (David R. Tyler).

I. Introduction.

II. General Overview of Polymer Photodegradation.

A. The Auto-Oxidation Mechanism.

B. Reactions of Hydroperoxide Species That Lead to Backbone Degradation.

C. Other Photochemical Degradation Mechanisms.

D. Methods for Intentionally Making Polymers Photodegradable.

III. Metal–Metal Bond-Containing Polymers.

A. Synthesis and Characterization.

B. Synthesis of the Difunctional Dimers.

C. Synthesis of the Polymers.

D. Characterization of the Polymers.

E. Photochemical Reactions in Solution.

F. Photochemistry in the Solid State.

IV. Factors Controlling the Rate of Photochemical Degradation.

A. Cage Effects.

B. The Effect of Tensile Stress on Photodegradation.

i. Theories of Stress-Induced Photodegradation.

ii. Stress-Induced Changes in φhomolysis; the Plotnikov Hypothesis.

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

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

v. The Zhurkov Equation.

vi. Quantum Yields as a Function of Stress for Polymer 3.

C. Other Factors Affecting Photochemical Degradation Rates of Polymers.

i. Absorbed Light Intensity.

ii. Polymer Morphology.

iii. Oxygen Diffusion.

iv. Chromophore Concentration.

V. Acknowledgments.

VI. References.

5. Zirconocene and Hafnocene-Containing Macromolecules (Charles E. Carraher Jr.).

I. General.

II. Introduction.

III. Inorganic Supported Zirconocene and Hafnocene Catalysts.

IV. Other Supports.

V. Condensation Reactions with Monomeric Lewis Bases.

VI. Zirconocene and Hafnocene Reactions with Already Existing Polymers.

VII. Miscellaneous.

VIII. Summary.

IX. References.

6. Compositional and Structural Irregularities of Macromolecular Metal Complexes (Anatolii D. Pomogailo, Gulzhian I. Dzhardimalieva).

I. Introduction.

II. Basic Transformations of Macroligands in Binding MXn.

A. Conformational Changes in Polymer Chains.

B. Macroligand Structuring Processes.

C. Macroligand Decomposition in MXn–Polymer Systems.

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

III. Transformation of Transition Metal Compounds in Reactions with Polymers.

A. Oxidation–Reduction Conversion of Transition Metals.

B. Monomerization of Transition Metal Dimer Complexes in Reactions with Polymers.

C. Composite Inhomogeneity of Macromolecular Complexes.

IV. Problem of Topochemistry of Macromolecular Complexes.

A. Topochemistry of Polymer Macroligand Functional Layers.

B. Topochemistry of Diamagnetic Complexes That Are Fixed to the Polymers.

C. Topochemistry of Polymer-Bonded Paramagnetic Complexes.

D. The Main Data on MMC Topochemistry.

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

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

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

C. Unit Variability Due to the Presence of Stable Metal Isotopes.

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

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

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

G. Exchange Interactions Between Metal Ions Incorporated in the Chain.

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

I. Stereoregularity of Metallopolymeric Chains.

J. Unit Variability Due to Chirality in Pendant Groups.

K. Unsaturation and Structurization of Metallopolymers.

L. Cyclization During Polymerization.

VI. Some Practical Applications of Unit Variability of Metal-Containing Polymers.

VII. Acknowledgments.

VIII. References.


"This book is well written and is readily accessible to readers of all levels…an excellent introduction to new researchers and a good reference for those more familiar with this field of study." (Journal of the American Chemical Society, May 3, 2006)