David A. Vicic, W. Jones
Aug 3, 1999
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Journal
Journal of the American Chemical Society
Abstract
The nickel hydride dimer [(dippe)NiH]2 (1) was found to react with a variety of organosulfur substrates under mild conditions leading to C−S bond insertion adducts. The transition-metal insertions into the C−S bonds of thiophene, benzothiophene, and dibenzothiophene are all reversible, and lead to new organometallic complexes when dissolved in hydrocarbon solvent. (dippe)Ni(η2-C,S-dibenzothiophene) (6) converts to four new organometallic species in a unique desulfurization reaction that is believed to proceed via the intermediacy of the late-metal terminal sulfido complex (dippe)NiS (23). Independent synthetic routes to the desulfurization products have also provided an entry into the preparation of a variety of nickel−sulfur complexes such as (dippe)Ni(SH)2, (dippe)2Ni2(μ-H)(μ-S), [(dippe)2Ni2(μ-H)(μ-S)][PF6], and [(dippe)Ni(μ-S)]2, all of which have been structurally characterized. The reactivity of 1 with 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene, 1,9-dimethyldibenzothiophene, thioxanthene...