Preparation of mononuclear and dinuclear Rh hydrotris(pyrazolyl)borato complexes containing arenethiolato ligands and conversion of the mononuclear complexes into dinuclear Rh-Rh and Rh-Ir complexes with bridging arenethiolato ligands

Reactions of Tp*Rh(coe)(MeCN)](; Tp*= HB(3,5-dimethylpyrazol-1-yl)(3); coe = cyclooctene) with one equiv. of the organic disulfides, PhSSPh, TolSSTol (Tol = 4-MeC(6)H(4)), PySSPy (Py = 2-pyridyl), and tetraethylthiuram disulfide in THF at room temperature afforded the mononuclear Rh(III) complexes Tp*Rh(SPh)(2)(MeCN)](3a), Tp*Rh(STol)(2)(MeCN)](3b), Tp*Rh(eta(2)-SPy)(eta(1)-SPy)](6), and Tp*Rh(eta(2)-S(2)CNEt(2))(eta(1)-S(2)CNEt(2))](7), respectively, via the oxidative addition of the organic disulfides to the Rh(I) 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)(micro-STol)(2)](5) was also obtained in low yield. Complex 3 was treated further with the Rh(III) or Ir(III) complexes (Cp*MCl)(2)(micro-Cl)(2)](Cp*=eta(5)-C(5)Me(5)) in THF at room temperature, yielding the thiolato-bridged dinuclear complexes Tp*RhCl(micro-SPh)(2)MCp*Cl](8a: M = Rh, 8b: M = Ir). Dirhodium complex TpRhCl(micro-STol)(2)RhCp*Cl](9) was obtained similarly from 4 and (Cp*RhCl)(2)(micro-Cl)(2)]. Anion metathesis of 8a proceeds only at the Rh atom with the Cp* ligand to yield Tp*RhCl(micro-SPh)(2)RhCp*(MeCN)]PF(6)](10), when treated with excess KPF(6) in CH(2)Cl(2)-MeCN. The X-ray analyses have been undertaken to determine the detailed structures of 3b, 4, 5, 6, 7, 8a, 9, and 10.