TY - JOUR
T1 - The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane
AU - Herberhold, Max
AU - Hill, Anthony F.
PY - 1990/9/25
Y1 - 1990/9/25
N2 - 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)].
AB - 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)].
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U2 - 10.1016/0022-328X(90)85277-6
DO - 10.1016/0022-328X(90)85277-6
M3 - Article
AN - SCOPUS:0011622080
SN - 0022-328X
VL - 395
SP - 195
EP - 206
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -