Mechanistic Insights on the Hydrodesulfurization of Biphenyl-2-thiol with Nickel Compounds

作者：Torres Nieto Jorge; Brennessel William W; Jones William D; Garcia Juventino J^*

来源：Journal of the American Chemical Society, 2009, 131(11): 4120-4126.

DOI：10.1021/ja809457s

The reactivity of the nickel(I) dimer [(dippe)(2)Ni(mu-H)](2) (1) with biphenyl-2-thiol was explored with the aim of clarifying the key step of sulfur extrusion during the hydrodesulfurization process using dibenzothiophene (DBT). These reactions were monitored by variable temperature NMR experiments which allowed the complete characterization and isolation of [(dippe)(2)Ni(2)(mu-H)(mu-S-2-biphenyl)] (3). The latter compound evolves to the terminal nickel-hydride [(dippe)Ni (eta(1)-C-2-biphenyl)(H)] (4) and transient [(dippe)NiS] (5), to ultimately yield [(dippe)(2)Ni(2)(mu-S)] (2) and biphenyl as the resulting HDS products. The reactivity of 1 and biphenyl-2-thiol was examined using different ratios of reactants, which allowed preparation of [(dippe)Ni(eta(1)-S-biphenyl-2-thiolate)(2)] (6) when using an excess of this substrate. The reactivity of 6 with 1 was addressed, yielding compound 2 and an equivalent amount of biphenyl.

• 出版日期2009-3-25