Halfsandwich Complexes Containing the Tetrathiotungstate Chelate Ligand. Crystal and Molecular Structure of Cp*Rh(PMe3)[(μ‐S)2WS2] (Cp* = η5‐Pentamethylcyclopentadienyl)

Abstract

AbstractThe reactions of Cp*M(PMe3)Cl2 (M = Rh (1a), Ir (1b)) with (NEt4)2[WS4] led to the heterodimetallic sulfido‐bridged complexes Cp*M(PMe3)[(μ‐S)2WS2] (M = Rh (2a), Ir (2b)), whereas the dimers [Cp*MCl(μ‐Cl)]2 (M = Rh (4a), Ir (4b)) reacted with (NEt4)2[WS4) to give the known trinuclear compounds [Cp*M(Cl)]2(μ‐WS4) (M = Rh (5a), Ir (5b)). Hydrolysis of the terminal W=S bonds converts 2a, b into Cp*M(PMe3)[(μ‐S)2WO2] (M = Rh (3a), Ir (3b)). Salts of a heterodimetallic anion, A[CpMo(I)(NO)(WS4)] (6) (A+ = NEt4+, NPh4+) were obtained by reactions of [CpMo(NO)I2]2 with tetrathiotungstates, A2[WS4]. The complexes were characterized by IR and NMR (1H, 13C, 31P) spectroscopy, and the X‐ray crystallographic structure of Cp*Rh(PMe3)[(μ‐S)2WS2] (2a) has been determined. The bond lengths and angles in the coordinations spheres of Rh and W in 2a (Rh···W 288.5(1) pm) are compared with related complexes containing terminal [WS42—] chelate ligands.