Characterization and reaction studies of dimeric molybdenum(III) complexes with bridging dithiolate ligands. Catalytic reduction of acetylene to ethylene

Journal Article · Wed Aug 29 04:00:00 EDT 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00512a023· OSTI ID:6015331

DuBois, M R; Haltiwanger, R C; Miller, D J; Glatzmaier, G

The complexes (C/sub 5/H/sub 5/MoSC/sub n/H/sub 2n/S)/sub 2/ (where n = 2 and 3) have been prepared by the reaction of ethylene sulfide and propylene sulfide, respectively, with C/sub 5/H/sub 5/MoH(CO)/sub 3/ or with (C/sub 5/H/sub 5/Mo(CO)/sub 3/)/sub 2/. Cyclic voltammetry shows that each complex undergoes two reversible oxidations at 0.13 and 0.79 V vs. SCE (in acetonitrile with 0.1 M Bu/sub 4/NBF/sub 4/). Both the one-electron and two-electron oxidation products have been synthesized and characterized by spectral and magnetic data. Electrochemical data for the oxidized complexes support the conclusion that the complexes have the same gross structural features in all three oxidation states. A single crystal of the monocation (C/sub 5/H/sub 5/MoSC/sub 3/H/sub 6/S)/sub 2/BF/sub 4/ has been characterized by an x-ray diffraction study. The compound crystallizes in the space group C2/c with a = 18.266 (1) A, b = 9.206 (4) A, c = 12.911 (5) A, ..beta.. = 100.83 (3)/sup 0/, and V = 2128 A/sup 3/. The metal ions of the cation are bridged by two 1,2-propanedithiolate ligands. The four sulfur atoms of these ligands form a plane which bisects the metal-metal distance. The neutral dimeric complexes undergo a unique reaction with alkenes and alkynes in which the hydrocarbon portion of the bridging dithiolate ligands is exchanged. The reaction has been characterized with olefinswith both electron-withdrawing and electron-donating substituents. When (C/sub 5/H/sub 5/MoSC/sub 2/H/sub 4/S)/sub 2/ (1) is reacted with acetylene at 25/sup 0/C, ethene is produced and the complex (C/sub 5/H/sub 5/MoSC/sub 2/H/sub 2/S)/sub 2/ is isolated. The latter complex is reduced by hydrogen (2 atm) at 60/sup 0/C to re-form 1. The utility of these reactions in the catalytic reduction of acetylene to ethylene has been investigated. The role of the sulfur ligands in this catalytic cycle is discussed. 50 references, 2 figures, 5 tables.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 6015331
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:18; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
ALKYNES
BOND ANGLE
BOND LENGTHS
BORON COMPLEXES
BRIDGES
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYOGENIC FLUIDS
CRYSTAL STRUCTURE
DATA
DATA FORMS
DIFFRACTION
DIMERS
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
HYDROCARBONS
HYDROGEN
INFORMATION
INFRARED SPECTRA
ISOLATED VALUES
LIGANDS
MAGNETIC PROPERTIES
MAGNETIC RESONANCE
MAGNETIC SUSCEPTIBILITY
MASS SPECTRA
MECHANICAL STRUCTURES
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
PHYSICAL PROPERTIES
RESONANCE
SCATTERING
SPACE GROUPS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
X-RAY DIFFRACTION