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Insertion Reactions of [M(SR)3(PMe2Ph)2] with CS2 (M = Ru, Os; R = C6F4H-4, C6F5). X-ray Structures of [Ru(S2CSC6F4H-4)2(PMe2Ph)2], trans-Thiolates [M(SR)2(S2CSR)(PMe2Ph)2] (M = Ru; R = C6F5 and M = Os; R = C6F4H-4), and trans-Thiolate−Phosphine [Os(SC6F5)2(S2CSC6F5)(PMe2Ph)2]

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posted on 09.02.2004, 00:00 by Maribel Arroyo, Sylvain Bernès, Joaquín Cerón, Jordi Rius, Hugo Torrens
Reactions of [M(SR)3(PMe2Ph)2] (M = Ru, Os; R = C6F4H-4, C6F5) with CS2 in acetone afford [Ru(S2CSR)2(PMe2Ph)2] (R = C6F4H-4, 1; C6F5, 3) and trans-thiolates [Ru(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 2; C6F5, 4) or the isomers trans-thiolates [Os(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 5; C6F5, 7) and trans-thiolate−phosphine [Os(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 6; C6F5, 8) through processes involving CS2 insertion into M−SR bonds. The ruthenium(III) complexes [Ru(SR)3(PMe2Ph)2] react with CS2 to give the diamagnetic thiolate−thioxanthato ruthenium(II) and the paramagnetic ruthenium(III) complexes while osmium(III) complexes [Os(SR)3(PMe2Ph)2] react to give the paramagnetic thiolate−thioxanthato osmium(III) isomers. The single-crystal X-ray diffraction studies of 1, 4, 5, and 8 show distorted octahedral structures. 31P {1H} and 19F NMR studies show that the solution structures of 1 and 3 are consistent with the solid-state structure of 1.