Activation of hydrogen by cationic cyclopentadienyl molybdenum dimers with sulfido ligands. 2. Cationic complexes derived from reactions with vinyl halides

Journal Article · Wed Oct 01 00:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00280a022· OSTI ID:5140872

Weberg, R T; Haltiwanger, R C; Laurie, J C.V.; DuBois, M R

The reaction of (CpMo-..mu..-S)/sub 2/S/sub 2/CH/sub 2/ (Cp = C/sub 5/H/sub 5/) with ..beta..-bromostyrene results in the formation of a ..beta..-phenyl-alkenylthiolate bridged cationic complex ((CpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-S)(..mu..-SC(H)C(H)Ph))Br, I. The product has been characterized by spectral methods and by an X-ray diffraction study. I crystallized in space group P2/sub 1//c with a = 13.325 (2) A, b = 15.868 (7) A, c = 25.901 (11) A, and ..beta.. = 98.30 (3)/sup 0/. The trans-vinylthiolate ligand is oriented in an equatorial configuration away from the sulfido ligand in the dimer. Complex I reacts with reducing agents to form a mixed valence molybdenum(III)/molybdenum(IV) derivative which rapidly disproportionates to (CpMo-..mu..-S)/sub 2/S/sub 2/CH/sub 2/ and a new molybdenum(III) dimer with two vinylthiolate ligands of the formula (CpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-SCHC(H)Ph)/sub 2/, III. Complex I reacts with hydrogen at 40/sup 0/C to form ethylbenzene and (CpMo-..mu..-S)/sub 2/S/sub 2/CH/sub 2/. Intermediates in this hydrogenolysis reaction have been detected by NMR and have been synthesized by alternate routes. They include the cation ((CpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-S)(..mu..-SC(H)(Me)Ph))Br, IV, and the neutral complex (CpMo)/sub 2/(S/sub 2/CH/sub 2/)(..mu..-SCH(Me)Ph)/sub 2/, V. Possible reaction pathways for the formation of these intermediates are discussed.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 5140872
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:20; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BROMIDES
BROMINE COMPOUNDS
CATIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMERS
ELEMENTS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROGEN
INFORMATION
IONS
LIGANDS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NMR SPECTRA
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REACTION INTERMEDIATES
RESONANCE
SCATTERING
SPACE GROUPS
SPECTRA
SYNTHESIS
THIOLS
TRANSITION ELEMENT COMPLEXES
VALENCE
X-RAY DIFFRACTION