The direct electrochemical synthesis of thiolato complexes of copper, silver, and gold the molecular structure of [Cu(SC6H4CH3-σ) (1,10phenanthroline)] 2CH3CN

Abstract

The electrochemical oxidation of anodic copper or silver (= M) into non-aqueous solutions of RSH (R = alkyl, axyl) gives M'SR as insoluble materials in high yield. In the presence of 1,lO-phenanthroline (= L), the products are M1sr for M = Cu, but not Ag. Gold resists oxidation under such conditions, and AU'SR (R = n-C4H9, C6H5) was obtained in only poor yield. The crystal structure of the solvated dimeric adduct [Cu(SC6H4CH3-o).phen]2.CH3isC Ntr iclinic, with α = 10.682(3) A, b = 11.729(4) A, c = 15.608(5) A, α = 76.87(2)", P = 76.35(2)", y = 68.07(2)", V = 1742(1) A3, Z= 2 and space group p i . The structure is based on a folded CuZS2r ing with an unusually s h Ct u -Cu distance of 2.613(3) A. Each copper atom has CuS2N2 pseudo-tetrahedral stereochemistry, with Cu-S = 2.337 A(av) and Cu-N = 2.10 A(av).