Alkoxides organometallic chemistry

The development of metal atom vapor technology over the last 15 years has made available to the chemist a new and useful synthetic technique. A number of novel transition metal compounds have been isolated by the method, particularly in the field of organometallic chemistry. However, the use of vaporized metal atoms for the synthesis of metal alkoxides and phenoxides by condensation into the neat alcohol has been only briefly mentioned in the literature.27... 

ORGANOMETALLIC CHEMISTRY SUPPORTED BY ALKOXIDE LIGANDS 15.3.6.1 Carbonyls of Molybdenum and Tungsten... 

Rothwell and Wolczanski have developed considerable titanium organometallic chemistry utilizing sterically hindered alkoxides as ancillary ligands. 

The dinuclear d3-d3 (RO)3M=M(OR)3 alkoxide system has provided a fertile inorganic redox active and coordinatively unsaturated template for the development of organometallic chemistry via substrate activation. Some of these interesting reactions are depicted in Scheme 10 and Eqs. 239, 241, and 242. 

This would embrace alkoxides (ROM), carboxylate salts (RCOOM), amides (R,2NM) and other similar metallic salts of acidic organic compounds. Classical organometallic chemistry would then limit itself to those compounds containing a direct cr-bond between carbon and a metal. 

Since a discussion of the properties and structures of metal alkoxides is essential for an understanding of the chemical processes during hydrolytic polycondensation, a short introduction to the chemistry of metal alkoxides is given first. This overview is restricted to the alkoxides of the network forming elements relevant to sol-gel processing (i.e., alkali and alkaline earth alkoxides, organometallic alkoxides, or alkoxides with metal-metal multiple bonds are not treated) excluding silicon. Three comprehensive books on metal alkoxides have appeared. ... 

In this book all these types of compounds will be considered, even though some, e.g. alkali metal amides and alkoxides, might not contain direct metal-carbon bonds. This is line with other books of organometallic chemistry (e.g. the multivolume treatise Comprehensive Organometallic Chemistry) which includes such... 

Alcohols and phenols form readily alkoxides and phenoxides. Organometallic chemistry is making use of metal ammonia solutions inter alia to prepare compounds containing metal-metal bonds ... 

The efficient syntheses of IVa allows an effective access to the organometallic chemistry of the Tbf moieties. Using the remarkable r -coordinated lithium salts y and VI, monosubstituted titanium(IV) alkoxides and aryloxides become available. The Tbf moiety is coordinated as a sterically demanding Cp derivative in an ii fashion to the titanium centers. The formal benzannula-tion of the fluorenyl system, as present in the Tbf titanium complexes, leads to large mono Cp complexes of high thermal stability compared to ii -fluorenyl titanium derivatives. Due to its heUcal twist, the T -coordinated Tbf ligands show Cl symmetry in the solid state but seem to interconverse in solution. Additionally, the titanium complexes were subjected to polymerization experiments of styrene to some extent. 

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