The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

Abstract

The complexes [MLn(PPh3)2(OSN-SO2C6H4Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [MLn(PPh3)2] or the corresponding tris(phosphine)compounds [MLn(PPh3)3]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d-orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh3)2(OSNSO2C6H4Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh3)3]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh3)2(OSN-SO2C6H4Me-4)]. Show more