Complexes of the platinum metals. Part VI. Dithiocarbamato- and O-alkyl dithiocarbonato-derivatives of ruthenium, osmium, and iridium
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 13,p. 1367-1372
- https://doi.org/10.1039/dt9750001367
Abstract
New dithiocarbamato- and O-alkyl dithiocarbonato-derivatives, [M(S–S)2(PPh3)2], [M(S–S)2(CO)(PPh3)], [MH(S–S)(CO)(PPh3)2](M = Ru or Os; S–S = R2NCS2 – or ROCS2 –; R = Me or Et), [OsCl(S2CNR2)(CO)(PPh3)2], and [IrH2(S–S)(PPh3)2], have been prepared by treating the appropriate chloro- orcarboxylato-complexes with sodium salts of the ligand. In several instances, hydride ligands, present in the parent complex, are also replaced by S–S groups. Tetramethylthiuram disulphide reacts with [IrCl(CO)(PPh3)2], [RuH2(PPh3)4], and [RuH2(CO)(PPh3)3] or [RuHCl(CO)(PPh3)3] to afford the complexes [Ir(S2CNMe2)2(CO)(PPh3)]Cl, [Ru(S2-CNMe2)2(PPh3)2], and [Ru(S2CNMe2)2(CO)(PPh3)] respectively. Structural and stereochemical assignments based on n.m.r. and i.r. spectroscopic data for the R2NCS2 – and ROCS2 – complexes confirm the expected substantial barrier to rotation about the S2C–NR2 bond in the former, but reveal no evidence of a comparable barrier to rotation about the S2C–OR bond in the latter.Keywords
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