Reactions of NaSPh with [Rh(PMe3)4]Cl and with RhCl(PMe3)3 give Rh(SPh)(PMe3)3 (1), whose X-ray crystallography shows a square-planar coordination. Temperature-dependent NMR ( and 31P{'H}) spectra of 1 show fluxionality of the molecule due to intramolecular exchange of the ligands in the solution. Complex 1 reacts smoothly with air to give the dioxygen-coordinated complex Rh(SPh)(02)(PMe3)3 (2). X-ray crystallography shows a distorted trigonal bipyramidal coordination around the metal center having a dioxygen ligand with the 0-0 bond distance of 1.456(6) Á. Addition of air to the reaction mixture of [Rh(PMe3)4]Cl with NaSCelL-p-OMe gives the analogous dioxygen-coordinated complex Rh(SC6H4-p-0Me)(02)(PMe3)3 (3). Reaction of complex 1 with HSPh in hexane causes oxidative addition of the S-H bond to the metal center to give the Rh(III) complex cií, wer-RhH(SPh)2(PMe3)3 (4a) as the initial product. Further stirring of the reaction mixture at room temperature causes isomerization of 4a into ironj,mer-RhH(SPh)2(PMe3)3 (4b). NMR ( and 31P) spectra of the complexes 4a and 4b as well as X-ray crystallography of 4b indicate their respective structures unambiguously. Reaction of
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