Modeling the hydrodesulfurization reaction of nickel. Unusual reactivity of dibenzothiophenes relative to thiophene and benzothiophene

Journal Article · Wed Aug 25 04:00:00 EDT 1999 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja9905997· OSTI ID:20000133

Vicic, D A; Jones, W D

The nickel hydride dimer [(dippe)NiH]{sub 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({eta}{sup 2}-C,S-dibenzothiophene) 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)Ni=S. 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){sub 2}, (dippe){sub 2}Ni{sub 2}({mu}-H)({mu}-S), [(dippe){sub 2}Ni{sub 2}({mu}-H)({mu}-S)][PF{sub 6}], and [(dippe)Ni{mu}-S]{sub 2}, all of which have been structurally characterized. The reactivity of 1 with 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene, 1,9-dimenthyldibenzothiophene, thioxanthene, and thianthrene is also presented.

• Research Organization: The Univ. of Rochester, NY (US)
• OSTI ID: 20000133
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 121; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
CHEMICAL REACTION KINETICS
DESULFURIZATION
DIMERS
NICKEL HYDRIDES
ORGANOMETALLIC COMPOUNDS
THIONAPHTHENES