Metal complexes of sulphur ligands. Part IX. Synthesis of dimethylphosphinodithioato-complexes of ruthenium(II) containing bidentate donor ligands

Abstract
The tris(chelate) complexes [Ru(S2Pme2)2(diene)]{diene = bicyclo[2.2.1]hepta-2,5-diene (nbd) or cyclo-octa-1,5-diene (cot)} have been synthesised by the reaction of [{RuCl2(diene)}n] with Na[S2Pme2]·2H2O in either ethanol or NN-dimethylformamide. The labile diene moiety is readily replaced by various chelating ligands to give [Ru(S2Pme2)2(L–L)]{L–L = Ph2P[CH2]2PPh2(dppe), Ph2PCH2PPh2(dppm), C6H4(AsMe2)2(pdma)}. For L–L = pdma, trans-[Ru(S2Pme2)2(pdma)2] is also formed. Unlike the corresponding cis-[Ru(S2Pme2)2L2][L = PR3 or P(OR)3], all the tris(chelate) complexes exhibit very slow rates of optical inversion and this evidence is used to tentatively propose a modified inversion mechanism of that postulated earlier.

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