Insertion reactions of carbon dioxide and carbon disulfide into alkyl-copper bonds of alkylcopper(I) Complexes having tertiary Phosphine ligands

Abstract

Alkylcopper(l) complexes with triphenylphosphine ligands (alkyl = Me, Et, n-Pr, i-Bu) react with carbon dioxide to give carboxylato complexes, (RCOO)Cu(PPh 3) 2 and two types of CO 2 adducts, (RCOO)Cu(CO 2)(PPh 3) 2 and Cu 2(CO 2)(PPh 3 2- (C 6H 4PPh 2). Similar reactions with carbon disulfide yield dithiocarboxylato complexes, (RCSS)Cu(PPh 3) 2. Alkylcopper complexes with 1,2-bis(diphenylphosphinoethane),(RCu) 2(dpe) 3, also react with carbon dioxide and carbon disulfide to afford insertion products of CO 2 and CS 2 into alkyl-copper bonds. Boiling of (RCSSCu) 2(dpe) 3 in CS 2 causes P-C bond cleavage in the dpe ligand and gives Cu(CS 2)(PPh 2)(dpe) 3 together with dithiocarboxylic acid and diphenylvinylphosphine. All the isolated complexes were characterized by elemental analyses, IR and NMR spectroscopy and chemical reactions.