A LINEAR, MONOMERIC COPPER(I) ACETATE DERIVATIVE, [CU(PHEN)2]2[CU(O2CCH3)2].(O2CCH3)2H - AN EFFECTIVE CATALYST FOR THE DECARBOXYLATION OF CARBOXYLIC-ACIDS

The complex [Cu(phen)2]2[Cu(O2CCH3)2].(O2CCH3)2H, derived from the reaction of CuO2CCH3 with 1,10-phenanthroline in dichloromethane, has been characterized by X-ray crystallography at -80-degrees-C. The crystals are monoclinic, space group C2/c with unit cell dimensions a = 22.503 (11) angstrom, b = 14.066 (6) angstrom, c = 16.829 (11) angstrom, beta = 112.44 (4)-degrees, V = 4923 (5) angstrom3, Z = 4, and R(F) = 6.52%. The compound is shown to have the above stoichiometry, containing a unique, linear, mononuclear copper(I) acetate anion. The monodentate coordination of the acetates results in Cu2-O1 and Cu2-O1a distances (2.808 angstrom); which are significantly greater than those observed for the corresponding bonding interactions between Cu2-O2 and Cu2-O2a (1.821 (8) angstrom). The title complex was observed to be an extremely effective catalyst or catalyst precursor for the homogeneous decarboxylation of the carboxylic acids cyanoacetic and 9-fluorenecarboxylic acids.