Reactions of [Tp*Rh(coe)(MeCN)]
(1; Tp*
= HB(3,5-dimethylpyrazol-1-yl)3; coe = cyclooctene) with one equiv. of the organic disulfides, PhSSPh, TolSSTol (Tol = 4-MeC6H4), PySSPy (Py = 2-pyridyl), and tetraethylthiuram disulfide in THF at room temperature afforded the mononuclear RhIII complexes [Tp*Rh(SPh)2(MeCN)]
(3a), [Tp*Rh(STol)2(MeCN)]
(3b), [Tp*Rh(η2-SPy)(η1-SPy)]
(6), and [Tp*Rh(η2-S2CNEt2)(η1-S2CNEt2)]
(7), respectively, via the oxidative addition of the organic disulfides to the RhI center in 1. For the Tp analogue [TpRh(coe)(MeCN)]
(2, Tp = HB(pyrazol-1-yl)3), the reaction with TolSSTol proceeded similarly to give the bis(thiolato) complex [TpRh(STol)2(MeCN)]
(4) as a major product but the dinuclear complex [{TpRh(STol)}2(μ-STol)2]
(5) was also obtained in low yield. Complex 3 was treated further with the RhIII or IrIII complexes [(Cp*MCl)2(μ-Cl)2]
(Cp*
=
η5-C5Me5) in THF at room temperature, yielding the thiolato-bridged dinuclear complexes [Tp*RhCl(μ-SPh)2MCp*Cl]
(8a: M = Rh, 8b: M = Ir). Dirhodium complex [TpRhCl(μ-STol)2RhCp*Cl]
(9) was obtained similarly from 4 and [(Cp*RhCl)2(μ-Cl)2]. Anion metathesis of 8a proceeds only at the Rh atom with the Cp* ligand to yield [Tp*RhCl(μ-SPh)2RhCp*(MeCN)][PF6]
(10), when treated with excess KPF6 in CH2Cl2–MeCN. The X-ray analyses have been undertaken to determine the detailed structures of 3b, 4, 5, 6, 7, 8a, 9, and 10.