Structural properties and inversion mechanisms of [Rh(dippe)(μ-SR)]2 complexes
摘要:
Several new bis-thiolate complexes of the type [Rh(dippe)(mu-SR)](2) where R = H, methyl, cyclohexyl, o-biphenyl, and phenyl, or (SR)(2)=SCH2CH2CH2S have been synthesized and characterized by NMR spectroscopy and single crystal X-ray diffraction. All [Rh(dippe)(mu-SR)](2) Complexes except [Rh(dippe)(mu-SPh)](2) exhibit bent geometries, while the orientation of the thiolato substituents changes with increasing steric bulk. H-1 and P-31 NMR spectroscopies indicate that both ring inversion and sulfur inversion occur among the members of the series, which allows them to access several isomeric forms when they are in solution. I I P NMR spectroscopy indicates that sulfur inversion in [Rh(dippe)(mu-SH)](2), [Rh(dippe)(mu-Sbiphenyl)](2), and [Rh(dippe)(mu-SPh)](2) is a non-dissociative process. (C) 2003 Elsevier B.V. All rights reserved.