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Thiourea monoanion and dianion complexes of rhodium(III) and ruthenium(II)

2002; Elsevier BV; Volume: 338; Linguagem: Inglês

10.1016/s0020-1693(02)01017-4

1873-3255

William Henderson, Brian K. Nicholson, M.B. Dinger, R. L. Bennett,

Metal complexes synthesis and properties

The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III) complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(μ-Cl)]2 [M=Rh, L=η5-C5Me5 (Cp*); M=Ru, L=η6-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives the dinuclear complexes [LM{SC(NCN)NMe}]2 containing chelate-bridging thiourea dianion ligands. The Ru complex was characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(NCN)NMe}(PPh3)] and [Cp*Rh{SC(NPh)NPh}(PPh3)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of triphenylphosphine. Reaction of [Cp*Rh{SC(NCN)NMe}(PPh3)] with HCl, or [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 and Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(NCN)NHMe}(PPh3)], containing a (monodentate) S-bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh3 and SbPh3 analogues of this complex were also prepared and characterised. Reaction of [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 or SbPh3 and PhNHC(S)NHPh or various trisubstituted thioureas PhNHC(S)NR1R2, triethylamine and NaBPh4 gave a range of cationic complexes [Cp*Rh{SC(NR1R2)NPh}(EPh3)]+ (E=P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex [Cp*Rh{SC(N(CH2CH2)2O)NPh}]2(μ-η2-dpph) (BPh4)2.