Reductive coupling, metal atom-organic complexes

Abstraction, reductive coupling, electron transfer, bond activation, oxidative addition, n-complexation, disproportionation and metal cluster formation are some of the reactions that occur when metal atoms interact with organic polymers and small molecules. Examples of these reactions are provided from the literature on the organometallic chemistry of free atoms and coordination-deficient molecules. Past uses of model compound studies to understand the early stages of chromium metallization on polyimide are critiqued. New evidence for reactions of chromium atoms with compounds related to polyimides is given. 

Insertion of carbon monoxide followed by reductive coupling is an old reaction that continues to be studied and developed. Examples of this reaction are the carbonylation of nickel dialkyl complexes to give ketones, " alkyl-alkoxides to yield esters, and alkyl-amides to give organic amides (Equation (79)). The carbonylation of the binuclear complex 145 leads to the formation of an isoquinolone ring with the elimination of one of the two Ni atoms, but no GO insertion occurs at the second metal moiety. Hydrolytic cleavage of the remaining Ni-G bond provides the free heterocyclic base (Scheme 45). ... 

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