Polynuclear Sulfide-Bridging Rh(III) Complexes with P(CH2OH)3

Abstract

A reaction of RhCl₃·3H₂O with P(CH₂OH)₃ (THP) and H₂S in methanol results in the formation of a new trinuclear complex [Rh₃(μ3-S)₂(μ₂-S)(μ₂-Cl)₂(THP)₆]Cl (1) with a yield of 29%. The structure of 1 is determined by X-ray crystallography. With the same initial compounds with hexamethyldisilthiane as a sulfide source a binuclear [Rh₂(μ₂-S₂)(μ₂-S)(THP)₆]²⁺ complex is obtained in which mono- and disulfide bridges are present simultaneously. The latter is isolated and structurally characterized as [Rh₂(μ-S₂)(μ₂-S)(THP)₆][Mo₆Cl₁₄]·0.6MeOH (2) with a yield of 12%. The compounds obtained are characterized by mass spectrometry and ³¹P NMR spectra.