Synthesis and reactivity of a dimeric molybdenum(III) complex with a bridging hydrosulfido ligand

Journal Article · Wed Sep 03 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00278a019· OSTI ID:5228438

Casewit, C J; DuBois, M R

A (cyclopentadienyl)molybdenum(III) dimer with a bridging hydrosulfido ligand (MeCpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-SCH/sub 3/)(..mu..-SH) (3) (MeCp = CH/sub 3/C/sub 5/H/sub 4/) has been synthesized by an unusual reaction of molecular hydrogen with the paramagnetic species (MeCpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-SCH/sub 3/)(..mu..-S) (5). Mechanistic features of this reaction are discussed. Complex 3 has been characterized by spectral methods, and the reactivity of the hydrosulfido ligand has been investigated. The ligand is deprotonated by methoxide ion and alkylated by alkyl halides in the absence of base. Activated alkenes and alkynes insert into the S-H bond of the ligand in the absence of base to form new dimers with alkyl and alkenyl thiolate ligands. The regio- and stereochemistries of the products of these reactions have been characterized and compared to those of reactions of the conjugate base of 3, which has been synthesized independently. Complex 3 also serves as a hydrogen atom transfer agent to certain unsaturated molecules. The relevance of these systems as models for the hydrodesulfurization catalysts is discussed.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 5228438
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:18; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
DATA
DESULFURIZATION
DIMERS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
LIGANDS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
PERFORMANCE
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES