Organometallic compounds, metal alkoxides synthesis

In this section, we will highlight the development in the use of metal alkox-ides for the synthesis of new and interesting organometallic compounds, many of these are either inaccessible or difficult to synthesize by common synthetic procedures. We will not discuss (a) the chemistry of organometallic compounds containing alkoxides as supporting ligands, for which excellent reviews by Chisholm and co-workers (154, 513, 514) are available and (b) intramolecular cyclometalation (i.e., C—H bond activation) reactions of metal aryloxides due to the availability of an excellent account of this topic in a review article by Rothwell (515). Furthermore, a brief mention of the use of a related metal derivative (i.e., metal aryloxide) will be made merely for comparison. 

Above all, the discovery that some organometallic compounds are effective in the synthesis of high molecular weight PCL [7] promoted a renewed interest in the ROP of lactones, particularly with alkyl metals, metal halides, oxides, car-boxylates, and alkoxides. These metal compounds were first classified as anionic... 

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... 

A large variety of organometallic compounds, e.g., metal alkoxides and metal carboxylates, has been studied as initiators or catalysts in order to achieve effective polymer synthesis [35]. Many reactions catalyzed by metal complexes are highly specific and, by careful selection of metal and ligands, reactions can be generated to form a desired polymer structure [36, 37]. The covalent metal alkoxides with freep or d orbitals react as coordination initiators and not as anionic or cationic inititors [38]. Fig. 1 summarizes some of the most frequently used initiators and catalysts. 

Although the development of metal atom vapour technology over the past three decades has shown tremendous utility for the synthesis of a wide range of organometallic compounds (many of which were inaccessible by conventional techniques), the use of this technique for the synthesis of metal alkoxides and related derivatives does not appear to have been fully exploited. In 1990, Lappert et al. demonstrated the utility of this technique for the synthesis of M—O—C bonded compounds by the isolation of alkaline earth metal aryloxides. 

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