Organometallic Reactions and Syntheses: Volume 6

ISBN-13: 9781461342281 / Angielski / Miękka / 2011 / 314 str.

E. I. Becker

Opis

The primary literature on organometallic chemistry has undergone phenomenal growth. The number of papers published from 1951 to 1976 is about equal to all prior literature. Together with this intense activity there has developed a complexity in the literature. Thus, specialized texts and teaching texts, a review journal, an advanced series, and a research journal have all appeared during this period. The present series also reflects this growth and recognizes that many categories of organometallic compounds now have numerous representatives in the literature. The purpose of Organometallic Reactions and Syntheses is to provide complete chapters on selected categories of organometallic compounds, describing the methods by which they have been synthesized and the reactions they undergo. The emphasis is on the experimental aspects, although struc tures of compounds and mechanisms of reactions are discussed briefly and referenced. Tables of all of the compounds prepared in the category under consideration and detailed directions for specific types make these chapters particularly helpful to the preparative chemist. While the specific directions have not been referenced in the same way. as are those in Organic Syntheses and Inorganic Syntheses, the personal experiences of the authors often lend special merit to the procedures and enable the reader to avoid many of the pitfalls frequently encountered in selecting an experimental procedure from the literature."

Spis treści

1 Vinyl Polymerization of Organic Monomers Containing Transition Metals.- I. Introduction and Scope.- II. Polymerization and Copolymerization of Vinyl Monomers Containing Ferrocene.- A. Homopolymerization.- B. Copolymerization of Vinylferrocene.- C. Isopropenylferrocene Polymerization.- D. Acrylic Ferrocene Monomers.- E. Miscellaneous Ferrocene Monomers.- III. Polymerization and Copolymerization of Ethynylferrocene.- IV. Polymerization and Copolymerization of Vinyl Organometallic Carbonyl Derivatives.- A. Vinylcyclopentadienyltricarbonylmanganese.- B. Monomers with ?6-Phenyltricarbonylchromium Groups.- C. ?4-(2,4-Hexadiene-1-yl acrylate)tricarbonyliron.- D. Titanium Acrylates.- V. Polymerization of 1,1?-Disubstituted Ferrocenes.- VI. Other Monomers.- VII. Example Monomer and Polymer Syntheses.- A. Homopolymerization of Vinylferrocene.- B. Copolymerization of Vinylferrocene.- C. Preparation of Isopropenylferrocene.- D. Synthesis and Homopolymerization of Ferrocenylmethyl Acrylate.- E. Synthesis and Homopolymerization of 1-Ferrocenyl-1,3-butadiene.- F. Synthesis and Polymerization of Ethynylferrocene.- G. Synthesis and Polymerization of Vinylcyclopentadienyltricarbonylmanganese.- H. Synthesis and Copolymerization of Styrenetricarbonylchromium.- I. Synthesis and Polymerization of Acrylic Monomers Containing ?6-Aryltricarbonylchromium.- J. Synthesis and Polymerization of ?4-(2,4-Hexadien-1-ylacrylate)tricarbonyliron.- K. Synthesis and Polymerization of 1,1?-Divinylferrocene.- L. Synthesis and Polymerization of trans-Chloro(4-vinylphenyl)-bis(tributylphosphine)palladium(II).- References.- 2 Reactions of Metallocarboranes.- I. Introduction and Scope.- II. Structures and Bonding.- A. General Observations.- B. Qualitative Bonding Descriptions.- C. Metallocarboranes as Metal Complexes.- D. Nomenclature and Numbering.- III. Synthetic Routes to Metallocarboranes.- A. General Observations.- B. Synthesis from Open-Cage Carboranes.- 1. Small Nido-Carboranes.- 2. C2B9H13 and C2B7H13.- 3. (CH3)4C4B8H8.- C. Synthesis from Polyhedral Carboranes.- 1. Methods and Starting Materials.- 2. Base Degradation.- 3. Reductive Cage Opening (Polyhedral Expansion).- 4. Polyhedral Contraction.- 5. Direct Metal Insertion.- 6. Metal Replacement in Metallocarboranes.- D. Synthesis from Metalloboranes.- E. Synthesis from Boranes.- F. Other Potential Routes to Metallocarboranes.- IV. Dicarbon, Tricarbon, and Tetracarbon Transition-Metal Metallocarboranes.- A. Titanium, Zirconium, and Vanadium Compounds.- B. Chromium, Molybdenum, and Tungsten Compounds.- 1. Twelve-Atom Cages.- 2. Thirteen-Atom Cages.- C. Manganese and Rhenium Compounds.- 1. Seven-Atom Cages.- 2. Nine-Atom Cages.- 3. Twelve-Atom Cages.- D. Iron Compounds.- 1. Six-, Seven-, and Eight-Atom Cages.- 2. Nine-, Ten-, and Eleven-Atom Cages.- 3. Twelve-Atom Cages.- 4. Thirteen-Atom Cages.- 5. Fourteen-Atom Cages.- E. Ruthenium Compounds.- F. Cobalt Compounds.- 1. General Comments.- 2. Six- and Seven-Atom Cages.- 3. Eight-, Nine-, and Ten-Atom Cages.- 4. Eleven-Atom Cages.- 5. Twelve-Atom Cages.- 6. Thirteen- and Fourteen-Atom Cages.- G. Rhodium Compounds. Catalytic Activity of 2,1,2- and 2,1,7-[(C6H5)3P]2Rh(H)C2B9H11.- H. Nickel Compounds.- 1. Seven- and Nine-Atom Cages.- 2. Ten-Atom Cages.- 3. Twelve-Atom Cages.- 4. Thirteen-Atom Cages.- I. Palladium and Platinum Compounds.- J. Copper Compounds.- K. Silver and Gold Compounds.- V. Monocarbon Transition-Metal Metallocarboranes.- A. Introduction.- B. Synthesis via Monocarbon Carborane Anions.- C. Synthesis via Carbonyl Insertion into B10H13?.- VI. Transition-Metal Phospha- and Arsametallocarboranes.- A. Synthetic Routes.- B. Manganese Compounds.- C. Iron Compounds.- D. Cobalt Compounds.- E. Nickel Compounds.- VII. Metallocarboranes of the Main-Group Metals.- A. Introduction.- B. Beryllium Compounds.- C. Aluminum, Gallium, Indium, and Thallium Compounds.- 1. General Comments.- 2. Seven-Atom Cages.- 3. Twelve-Atom Cages.- D. Germanium, Tin, and Lead Compounds.- 1. General Comments.- 2. Dicarbon-Cage Systems.- 3. Monocarbon-Cage Systems.- References.- 3 Homogeneous Catalysis by Arene Group-VIB Tricarbonyls.- I. Introduction.- II. Chemistry of Arene Group-VIB Tricarbonyls.- A. Displacement of the Arene Ring by Donor Molecules.- B. Ring Exchange with Other Aromatic Molecules.- C. Substitution on the Coordinated Arene.- D. Reactions on Functional Groups on the Coordinated Arene.- E. Substitution of CO.- F. Total Substitution of Arene and CO.- G. Addition and Oxidative Addition.- H. Summary.- I. Experimental Procedures.- III. Friedel-Crafts and Related Reactions.- A. Reactions Promoted by the Catalysts.- B. Experimental Features.- C. Nature of the Catalyst.- D. Type of Reaction.- E. Mechanism.- F. Related Reactions.- G. Experimental Procedures.- IV. Hydrogenation of Olefins.- A. Reactions Promoted by ArM(CO)3 and Related Catalysts.- B. Features of Hydrogenation.- C. Mechanism.- D. Experimental Procedures.- V. Isomerization of Olefins.- A. Reactions Promoted by ArM(CO)3 and Related Catalysts.- B. Discussion.- C. Mechanism.- D. Experimental Procedures.- VI. Olefin Metathesis.- A. Homogeneous Systems.- B. Heterogeneous Systems.- VII. Reactions of Acetylenes.- A. Trimerization.- B. Polymerization.- C. Experimental Procedures.- VIII. Polymer-Bound Systems.- A. Hydrogenation of Methyl Sorbate.- B. Friedel—Crafts Reactions.- C. Experimental Procedures.- References.