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

Abstract

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.

Addition of benzenethiol to terminal alkynes catalyzed by hydrotris(3,5-dimethylpyrazolyl)borate–Rh(III) bis(thiolate) complex: Mechanistic studies with characterization of the key intermediate

“…1 and Table 1. The Rh center of 3 adopts a slightly distorted octahedral geometry as observed for 2, whose structure has been previously confirmed by the X-ray analysis of the p-toluenethiolate analog [Tp * Rh(SC 6 H 4 Me-p) 2 (MeCN)] (2 0 ) [20]. Three Rh-N bond distances in 3 are almost the same, indicating that the trans influence of XyNC ligand is comparable to that of benzenethiolate.…”

“…(3)). Distorted structure of the rhodathiacyclobutene ring is quite similar to the 4-membered ring in [Tp * Rh(g 2 -S-2-C 5 H 4 N)(g 1 -S-2-C 5 H 4 N)] [20]. ( …”

“…The bis(thiolate) complex [Tp * Rh(SPh) 2 (MeCN)] (2) [20] was treated with several organic molecules to examine the reactivity at the metal center. When 2 was treated with excess XyNC at room temperature, the MeCN ligand in 2 was smoothly replaced by XyNC to form [Tp * Rh(SPh) 2 (XyNC)] (3).…”

“…We have recently reported the first reliable route to synthesize rhodium thiolate complexes with Tp ancillary ligands and their chalcogenolate congeners [20,21]. The Rh(I) complex [TpRh(coe)(MeCN)] (coe = g 2 -cyclooctene) and its hydrotris(3,5-dimethylpyrazolyl)-borate (Tp * ) analog [Tp * Rh(coe)(MeCN)] (1) [22] react with a range of organic disulfides to give mononuclear bis(thiolate) complexes, as exemplified in Eq.…”

Hydroelementation of Unsaturated C–C Bonds Catalyzed by Metal Scorpionate Complexes

“…Substitution of MeCN for XyNC on [Tp*Rh(SPh) 2 (MeCN)] generates [Tp*Rh(SPh) 2 (XyNC)]. [Tp*Rh( p ‐MeC 6 H 4 S) 2 (MeCN)] and [Tp*Rh(SPh) 2 (XyNC)] were both characterized in the solid state and show to adopt a distorted octahedral structure in which the Tp* is bound in a κ 3 coordination mode. The MeCN ligand could also be displaced by a variety of terminal acetylenes, resulting in a rhodathiacyclobutene structure which was also characterized in the solid state (Scheme ) …”