Metal complexes of sulphur ligands. Part III. Reaction of platinum(II)NN-dialkyldithiocarbamates, O-ethyl dithiocarbonate (xanthate), and OO′-diethyl dithiophosphate with tertiary phosphines
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 254-263
- https://doi.org/10.1039/dt9730000254
Abstract
Evidence is presented to show that the reaction of all M(S–S)2 compounds [M = Pt, Pd; (S–S)–=–S2CNR2(R = Me, Et), –S2COR (R = Et, PhCH2), –S2P(OEt)2, and –S2PR2(R = Me, Et, Ph)] with tertiary phosphines occurs by stepwise cleavage of metal–sulphur bonds to generate four-co-ordinate compounds of formulae [M(S–S)2PR′3] and [M(S–S)(PR′3)2](S–S) with unidentate/bidentate (III) and ionic/bidentate (IV) co-ordination respectively. All the ionic compounds readily revert to the [M(S–S)2PR′3] complexes in the presence of non-polar solvents via nucleophilic attack by (S–S)– on the metal. In addition, for (S–S)–=–S2COR, –S2P(OEt)2, nucleophilic attack can also occur on a co-ordinated alkoxy group to give the novel compounds [(R′3P)2MS2CO](I) and [(R′3P)2MS2P(O)OEt](II) respectively. For [M(S–S)(PR′3)2](S–S) compounds containing –S2CNR2, the presence of excess PR′3 catalyses the reaction between dithiocarbamate ion and dichloromethane, giving CH2(S2CNR2)2 and [M(S2CNR2)(PR′3)2]Cl, H2O. These conclusions are based on extensive physico-chemical studies and, in particular, the use of variable temperature 1H n.m.r. spectroscopy.Keywords
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