Metal complexes of sulphur ligands. Part 15. Reaction of bis[(η-arene)dichlororuthenium] and bis[dichloro(η-pentamethylcyclopentadienyl)metal] complexes of rhodium and iridium with various dithioacid ligands

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Abstract
Reaction of the complexes [{Ru(η-arene)Cl2}2](1)(arene = C6H6 or C6H3Me3) and [{M(η-C5Me5)Cl2}2](2)(M = Rh or Ir) with excess of various dithioacid anions gives monomeric [Ru(η-arene)(S–S)2](3; S–S–=[S2PR2]–) and [M(η-C5Me5)(S–S)2](4: M = Rh, S–S–=[S2PR2]–, [S2CNR2]–, or [S2COR]–; M = Ir, S–S–=[S2CNMe2]– or [S2PMe2]–) respectively. Analytical data together with i.r. and 1H, 13C, and 31P n.m.r. studies show that these complexes contain both bi- and uni-dentate dithioacid groups both in the solid state and in solution. For [M(η-C5Me5)(S2CNMe2)2](M = Rh or Ir) and [Rh(η-C5Me5)(S2COEt)2] in solution at higher temperatures, however, kinetic line-shape analysis indicates the occurrence of uni- and bi-dentate dithioacid exchange probably via a dissociatively controlled intramolecular mechanism. Reaction of (1; arene = C6H6) and (2; M = Rh) with [S–S]–(1 : 1 mol ratio) gives [Ru(η-C6H6)Cl(S2PPh2)] and [Rh(η-C5Me5)Cl(S–S)](5; S–S–=[S2NMe2]–,[S2PMe2]–, or [S2PPh2]–) respectively which are useful precursors for synthesising a range of complexes such as [Rh(η-C5Me5)X(S2CNMe2)](X = Br–, I–, or SCN–) and the mixed dithioacid complexes [Rh(η-C5Me5)(S2CNMe2)(S–S)](6; S–S–=[S2PMe2]–, [S2PPh2]–, or [S2COMe]–). In methanol, (5; S–S–=[S2CNMe2]–) gives the solvated cation [Rh(η-C5Me5)(HOMe)(S2CNMe2)]+ which reacts with various Lewis bases (L) to give [Rh(η-C5Me5)(S2CNMe2)L][BPh4](L = PPh3, PMePh2, CO, AsPh3, or C5H5N). Similar complexes can also be made by reaction of [Ru(arene)Cl2(NC5H5)] or [Rh(η-C5Me5)Cl2(PPh3)] with [S–S]–(1 : 1 mol ratio) and excess of Na[BPh4]. However, reaction of (5; S–S–=[S2CNMe2]–) with excess of Ph2P[CH2]PPh2(dppe) or Ph2PCH2PPh2(dppm) in methanol gives the dimeric cations [{Rh(ηC5Me5)(S2CNMe2)}2(dppe or dppm)]2+(7) and with C2(CN)4 and Na[BPh4] in methanol the cyanotriphenylborate complex [Rh(η-C5Me5)(NCBPh3)–(S2CNMe2)](8) is formed.

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