Synthesis, Reactions and Catalytic Properties of Stable Alkoxocopper, Phenoxocopper and Related Copper Complexes Containing Triphenylphosphine Ligands

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Abstract
A variety of new alkoxocopper and phenoxocopper(I) complexes containing triphenylphosphine ligands have been prepared by the reactions of methylbis(triphenylphosphine)copper(I) etherate (I) with the corresponding alcohols and phenols. The isolated complexes were characterized by elemental analysis, IR and NMR spectroscopy and chemical reactions. The reactions of the alkoxocopper and phenoxocopper complexes with alkyl halides and acyl halides or carboxylic anhydrides yield ethers and carboxylic esters, respectively. The stoichiometric exchange reactions of the alkoxo group in the alkoxocopper complexes with carboxylic esters proceed smoothly and the alkoxocopper complexes were found to act as excellent catalysts for the transesterifications between carboxylic esters and alcohols. The exchange reactions take place also between the alkoxocopper complexes and phenols or thiols producing phenoxocopper or alkylthiocopper complexes with the liberation of alcohols. Amides and nitromethane react with the alkoxocopper complexes releasing alcohols to give N-bonded amidocopper and O-bonded acinitrocopper complexes, respectively. The thermolysis of the alkoxocopper complexes in various solvents were studied and the mechanism and the factors influencing the course of thermolysis discussed.

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