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

by Abd-El-Aziz, Alaa S.; Carraher, Charles E.; Pittman, Charles U.; Zeldin, Martel

• ISBN13: 9780471684459
• ISBN10: 0471684457
• Format: Hardcover
• Copyright: 2005-11-04
• Publisher: Wiley-Interscience

Summary

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.

Author Biography

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.

Table of Contents

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