701255-90-5Relevant academic research and scientific papers
Structural properties and inversion mechanisms of [Rh(dippe)(μ-SR)] 2 complexes
Oster, Stephen S.,Jones, William D.
, p. 1836 - 1846 (2004)
Several new bis-thiolate complexes of the type [Rh(dippe)(μ-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)(μ-SR)]2 complexes except [Rh(dippe)(μ-SPh)] 2 exhibit bent geometries, while the orientation of the thiolato substituents changes with increasing steric bulk. 1H and 31P 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. 31P NMR spectroscopy indicates that sulfur inversion in [Rh(dippe)(μ-SH)] 2, [Rh(dippe)(μ-Sbiphenyl)]2, and [Rh(dippe)(μ-SPh)] 2 is a non-dissociative process.
Carbon-sulfur bond activation of dibenzothiophenes and phenoxythiin by [Rh(dippe)(μ-H)]2 and [Rh2(dippe)2(μ-Cl) (μ-H)]
Oster, Stephen S.,Grochowski, Matthew R.,Lachicotte, Rene J.,Brennessel, William W.,Jones, William D.
, p. 4923 - 4931 (2011/01/09)
The rhodium dimer [Rh(dippe)(μ-H)]2 (1) reacts with dibenzothiophene to form the C-S cleavage product [Rh2(dippe) 2(μ-SC12H9)(μ-H)] (3). Complex 1 also reacts with 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene to form [Rh2(dippe)2(μ-S-MeC12H8)(μ-H) ] (4) and [Rh2(dippe)2(μ-S-Me2C 12H7)(μ-H)] (6), respectively. Reaction with phenoxythiin forms [Rh2(dippe)2(μ-S-C6H 4OC6H5)(μ-H)] (8). In 3, rhodium addition to the ortho C-H bond of the β-ring of the biphenylthiolate substituent does not occur at 100 °C. The crystal structures of [Rh2(dippe) 2(μ-Cl)(μ-H)] (2), 4, 6, and 8 indicate that each complex contains a nearly planar Rh2(μ-X)(μ-H) core. The 1H NMR spectra of 3, 4, and 6 suggest that the pyramidal geometry at the sulfur atom is maintained in solution and that sulfur inversion is absent. Unreacted 1 catalyzes H/D exchange between C6D6 and the biphenylate substituent of 3 faster than it cleaves the remaining C-S bond to make free biphenyl. Complex 3 is unreactive toward excess dibenzothiophene, while [Rh 2(dippe)2(μ-Cl)(μ-H)] cleaves a C-S bond of DBT to form [Rh2(dippe)2(μ-Cl)(μ-SC12H 9)] (9).
