Desulfurization of dibenzothiophene by nickel(0) complexes: evidence for electron transfer in oxidative additions

Journal Article · Fri Sep 09 04:00:00 EDT 1983 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00166a005· OSTI ID:5507704

Eisch, J J; Hallenbeck, L E; Han, K I

Two equivalents of the complex (2,2'-bipyridyl)(1,5-cyclooctadiene)nickel(0) cleave dibenzothiophene in homogeneous media to form nickel-substituted biphenyl derivatives and nickel sulfide. The cleavage proceeds more readily in tetrahydrofuran (THF) than in benzene solution, and excess amine (either bipyridyl or pyridine) retards the reaction. Neither biphenylene nor 2-phenylbenzenethiol was a detectable transient in the desulfurization process. The possible fleeting formation of biphenylene was ruled out by a study of the desulfurized products obtained from the 2,8-dimethyl and the 3,7-dimethyl derivatives of dibenzothiophene. A possible role of nickel hydride in some of the C-S bond cleavage is suspected from the observed effects of either acid or lithium aluminum hydride (LiAlH/sub 4/) used in the workup of the reaction mixture. The reaction is not catalytic in nickel when an excess of LiAlH/sub 4/ is used; indicating that Ni(0) cannot be regenerated from NiS under these conditions. The observed cleavage of approx. 50% of the dibenzothiophene by 2 equiv of (2,2'-bipyridyl)(1,5-cyclooctadiene) nickel ((C/sub 10/H/sub 8/N/sub 2/)Ni(C/sub 8/H/sub 12/)) is ascribed to the gradual formation of bis(cyclooctadiene) nickel ((C/sub 10/H/sub 8/N/sub 2/)/sub 2/Ni) which is ineffectual in cleaving dibenzothiophene. Finally, the relative reactivity of the dibenzothiophenes (dibenzothiophene > 2,8-dimethyldibenzothiophene >> 3,7-dimethyldibenzothiophene), the relative effectiveness of amine donors or solvents, and the observed hydrogen abstraction from the solvent are interpreted in terms of an electron-transfer mode of action by the nickel(0) desulfurizing agent.

• Research Organization: State Univ. of New York, Binghamton
• DOE Contract Number: AC22-79ET14879; FG22-81PC40782
• OSTI ID: 5507704
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 48:18; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010402 -- Coal
Lignite
& Peat-- Purification & Upgrading
02 PETROLEUM
020800 -- Petroleum-- Waste Management
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400105* -- Separation Procedures
ACETIC ACID
ADDITIVES
ALKALI METAL COMPOUNDS
ALKENES
ALUMINIUM COMPOUNDS
ALUMINIUM HYDRIDES
AROMATICS
AZINES
BENZENE
BIPYRIDINES
CARBOXYLIC ACIDS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHROMATOGRAPHY
COMPLEXES
CYCLOALKENES
DATA
DESULFURIZATION
DIENES
ELECTRON TRANSFER
EXPERIMENTAL DATA
FORMIC ACID
FURANS
GAS CHROMATOGRAPHY
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
KINETICS
LITHIUM COMPOUNDS
LITHIUM HYDRIDES
MASS SPECTRA
MONOCARBOXYLIC ACIDS
NICKEL COMPLEXES
NICKEL COMPOUNDS
NICKEL SULFIDES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SOLVENTS
ORGANIC SULFUR COMPOUNDS
PHOSPHORIC ACID
POLYENES
PYRIDINE
PYRIDINES
REACTION INTERMEDIATES
REACTION KINETICS
SEPARATION PROCESSES
SOLVENTS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SULFIDES
SULFUR COMPOUNDS
TETRAHYDROFURAN
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
YIELDS