A series of thiolato-bridged di- and trinuclear complexes derived from [Tp∗Rh(SPh)2(MeCN)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate)

Treatment of the Rh(III) complex [Tp∗Rh(SPh)2(MeCN)] (1) with a series of late transition metal complexes resulted in the formations of thiolate-bridged di- and trinuclear complexes, which include the Rh(III)–Rh(I) complexes, [Tp∗RhCl(μ-SPh)2Rh(cod)] (2) and [Tp∗RhCl(μ-SPh)2Rh(PPh3)2], the Rh(III)–Pd(II) complexes, [Tp∗RhCl(μ-SPh)2Pd(η3-C3H5)] (4), [{Tp∗Rh(MeCN)}(μ-SPh)2PdCl2] (5), and [{Tp∗RhCl(μ-SPh)2}2Pd] (6), and the Rh(III)–Pt(II) complex [{Tp∗RhCl(μ-SPh)2}2Pt] (7). Early-late transition metal complexes containing the Rh(III)–Re(I) and Rh(III)–Mo(0) metal centers, [Tp∗RhCl(μ-SPh)2Re(CO)4] and [{Tp∗Rh(CO)}(μ-SPh)2Mo(CO)4] were also prepared from 1. The X-ray analysis has been carried out to confirm the structures for 2, 4, 5, 6, and 7.