New class of homoleptic 12-electron molybdenum and tungsten alkoxide clusters of formula (M/sub 4/(OR)/sub 12/)

Journal Article · Wed May 11 04:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00218a059· OSTI ID:7005334

Chisholm, M H; Folting, K; Hammond, C E; Hampden-Smith, M J

The authors are interested in developing efficient synthetic routes to alkoxide-supported molybdenum and tungsten clusters that may prove to be excellent models for fragments of reduced oxides of the same metals. These clusters should include both coordinative unsaturation and redox flexibility at the metal centers to initiate organometallic chemistry upon substrate reduction. Complementary metal oxide model systems such as polyoxoanions may prove effective for oxidation catalysis. They have recently demonstrated that W/sub 2/(O-i-Pr)/sub 6/ (I) exists in reversible equilibrium with its 12-electron cluster W/sub 4/(O-i-Pr)/sub 12/ (II) in solution at room temperature, eq 1, whereas Mo/sub 2/(O-i-Pr)/sub 6/ is indefinitely stable with respect to cluster formation. Even by reducing the steric demands at the molybdenum center they were unable to induce the formation of new metal-metal bonds in (Mo/sub 2/(O-i-Pr)/sub 5/(OMe))/sub 2/ (III), which instead retains isolated, unbridged Mo-Mo triple bonds. The authors report here the isolation and characterization of members of a new class of 12-electron tetranuclear alkoxide clusters, IV-XI, which are spectroscopically isostructural for both molybdenum and tungsten together with the single-crystal X-ray diffraction structure of one derivative, (Mo/sub 4/(O-CH/sub 2/-c-Bu)/sub 12/(HO-CH/sub 2/-c-Bu)) (XI) (where c-Bu = cyclobutyl). This represents the first group of structurally related homoleptic alkoxide clusters for molybdenum and tungsten in oxidation state (3+).

• Research Organization: Indiana Univ., Bloomington (USA)
• OSTI ID: 7005334
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:10; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
CARBON 13
CARBON ISOTOPES
CHEMICAL PREPARATION
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLYBDENUM COMPOUNDS
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
RESONANCE
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
VALENCE
X-RAY DIFFRACTION