A novel and easy way to prepare the Rh 2(μ-SR) 2(CO) 4 and Rh 2(μ-SR) 2(CO) 2(PR′ 3) 2 complexes on a large scale

Abstract

Large amounts of the tetracarbonyl starting material Rh 2(μ-SR) 2)(CO) 4 can be easily and quantitatively produced by addition of the thiol HSR onto the anion [RhCl 2(CO) 2] −, which is generated by reduction of hydrated rhodium trichloride in refluxing methanol under an atmosphere of CO. The μ-thiolato complexes can be isolated (R = Me, Ph, CH 2Ph, C 6F 5, t-Bu) and quantitatively transformed into the disubstituted complexes Rh 2(μ-SR) 2(CO) 2(PR′ 3) 2 by addition of two equivalents of the appropriate phosphine PR′ 3.