1036708-77-6Relevant articles and documents
Synthesis, structural characterization, and ligand replacement reactions of gem-dithiolato-bridged rhodium and iridium complexes
Rivas, Angel B.,Gascon, Jose M.,Lahoz, Fernando J.,Balana, Ana I.,Pardey, Alvaro J.,Oro, Luis A.,Perez-Torrente, Jesus J.
, p. 6090 - 6104 (2009/02/05)
The reaction of gem-dithiol compounds R2C(SH)2 (R = Bn (benzyl), iPr; R2 = -(CH2J4-) with dinuclear rhodium or iridium complexes containing basic ligands such as [M(μ-OH)(cod)]2 and [M(μ-OMe)(cod)]2, or the mononuclear [M(acac)(cod)] (M = Rh, Ir, cod = 1,5-cyclooctadiene) in the presence of a external base, afforded the dinuclear complexes [M 2(μ-S2CR2)(cod)2] (1-4). The monodeprotonation of 1,1-dimercaptocyclopentane gave the mononuclear complex [Rh(HS2Cptn)(cod)] (5) that is a precursor for the dinuclear compound [Rh2(μ-S2Cptn)(cod)2] (6). Carbonylation of the diolefin compounds gave the complexes [Rh2(M-S 2CR2)(CO)4] (7-9), which reacted with P-donor ligands to stereoselectively produce the trans isomer of the disubstituted complexes [Rh2(μ-S2CR2)(CO) 2(PR′3)2] (R′ = Ph, Cy (cyclohexyl)) (10-13) and [Rh2(μ-S2CBn 2)(CO)2{P(OR′)3}2] (R′ = Me, Ph) (14-15). The substitution process in [Rh2(μ-S 2CBn2)(CO)4] (7) by P(OMe)3 has been studied by spectroscopic means and the full series of substituted complexes [Rh2(μ-S2CBn2)(CO)4-n{P(OR) 3}n] (n = 1, 4) has been identified in solution. The eis complex [Rh2(μ-S2CBn2)(CO) 2(μ-dppb)] (16) was obtained by reaction of 7 with the diphosphine dppb (1,4-bis(diphenylphosphino)butane). The molecular structures of the diolefinic dinuclear complexes [Rh2(μ-S2CR 2)(cod)2] (R = Bn (1), iPr (2); R2 = -(CH2)4 - (6)) and that of the cis complex 16 have been studied by X-ray diffraction.
