Syntheses and Structures of Molybdenum, Tungsten, and Manganese Complexes of a Cyclic Thiourea, [M(CO)5(SC3N2Me4)] (M = Mo, W) and [{CpMn(CO)2}2(μ‐SC3N2Me4)

Abstract

AbstractPhotolysis of [CpMn(CO)3] in the presence of 1,3,4,5‐tetramethylimidazoline‐2‐thione, SC3N2Me4 (1), produced a thione‐bridged dinuclear complex, [{CpMn(CO)2}2(μ‐SC3N2Me4)] (2). Compound 2 shows unprecedented geometry of the Mn–S–Mn framework, featuring a pyramidal sulfur atom and long Mn···Mn distance. Photoreaction of [M(CO)6] (M = Mo, W) with 1 afforded mononuclear complexes [M(CO)5(SC3N2Me4)] [M = Mo (3), W (4)]. In compounds 2–4, the C–S bond of the thione ligand is stretched on coordination because of the polarization of the metal–ligand linkage. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)