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

The electrochemical oxidation of anodic copper or silver (= M) into non-aqueous solutions of RSH (R = alkyl, axyl) gives M I SR as insoluble materials in high yield. In the presence of 1,10-phenanthroline (= L), the products are M I SR • phen for M = Cu, but not Ag. Gold resists oxidation under such conditions, and Au I SR (R = n-C 4 H 9 , C 6 H 5 ) was obtained in only poor yield. The crystal structure of the solvated dimeric adduct [Cu(SC 6 H 4 CH 3 -o) • phen] 2• CH 3 CN is triclinic, with a = 10.682(3) Å, b = 11.729(4) Å, c = 15.608(5) Å, α = 76.87(2)°, β = 76.35(2)°, γ = 68.07(2)°, V = 1742(1) Å 3 , Z = 2 and space group [Formula: see text]. The structure is based on a folded Cu 2 S 2 ring with an unusually short Cu—Cu distance of 2.613(3) Å Each copper atom has CuS 2 N 2 pseudo-tetrahedral stereochemistry, with Cu—S = 2.337 Å(av) and Cu—N = 2.10 Å(av).