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

Abstract

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.

Authors:
;
Publication Date:
Research Org.:
The Univ. of Rochester, NY (US)
OSTI Identifier:
20000133
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 33; Other Information: PBD: 25 Aug 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; 02 PETROLEUM; ORGANOMETALLIC COMPOUNDS; DESULFURIZATION; NICKEL HYDRIDES; DIMERS; THIONAPHTHENES; CHEMICAL REACTION KINETICS

Citation Formats

Vicic, D.A., and Jones, W.D. Modeling the hydrodesulfurization reaction of nickel. Unusual reactivity of dibenzothiophenes relative to thiophene and benzothiophene. United States: N. p., 1999. Web. doi:10.1021/ja9905997.
Vicic, D.A., & Jones, W.D. Modeling the hydrodesulfurization reaction of nickel. Unusual reactivity of dibenzothiophenes relative to thiophene and benzothiophene. United States. doi:10.1021/ja9905997.
Vicic, D.A., and Jones, W.D. Wed . "Modeling the hydrodesulfurization reaction of nickel. Unusual reactivity of dibenzothiophenes relative to thiophene and benzothiophene". United States. doi:10.1021/ja9905997.
@article{osti_20000133,
title = {Modeling the hydrodesulfurization reaction of nickel. Unusual reactivity of dibenzothiophenes relative to thiophene and benzothiophene},
author = {Vicic, D.A. and Jones, W.D.},
abstractNote = {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.},
doi = {10.1021/ja9905997},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 33,
volume = 121,
place = {United States},
year = {1999},
month = {8}
}