Metal alkoxides: Models for metal oxides. 16. Synthesis and characterization of a new class of homoleptic 12-electron molybdenum and tungsten alkoxide clusters of formula M
- Indiana Univ., Bloomington (USA)
- Univ. of Durban-Westville (South Africa)
Addition of primary alcohols, RCH{sub 2}OH (> 6 equiv), to hydrocarbon solutions of M{sub 2}(O-t-Bu){sub 6} compounds has led to the isolation of the first homoleptic series of cluster alkoxides M{sub 4}(OCH{sub 2}R){sub 12} for both M = Mo and W where R = i-Pr, Cy (Cy = cyclohexyl), Cp (Cp = cyclopentyl), and c-Bu (c-Bu = cyclobutyl). The NMR data ({sup 1}H and {sup 13}C) indicate a common structural unit for this class of compounds containing a molecular mirror plane. For each M{sub 4}(OCH{sub 2}R){sub 12} compound there are eight types of alkoxide ligands in the integral intensity 2:2:2:2:1:1:1:1. Those having integral intensity two possess diastereotopic methylene protons, indicating that they do not lie on the mirror plane, whereas the other four alkoxides (1:1:1:1) are contained within the mirror plane. Though these compounds yield crystals from 1,2-dimethoxyethane, they failed to diffract beyond 10{degree} indicating a molecular disorder within hexagonal packing of M{sub 4} units. However, the cyclobutylmethoxide derivatives crystallize with an additional molecule of alcohol, M{sub 4}(CH{sub 2}-c-Bu){sub 12}(HOCH{sub 2}-c-Bu), and the molecular structure of the molybdenum compound was determined by an X-ray study. Crystal data for Mo{sub 4}(OCH{sub 2}-c-Bu){sub 12}(HOCH{sub 2}-c-Bu) at {minus}156{degree}C: a = b = 19.952 (7) {angstrom}, c = 34.755 (16) {angstrom}, Z = 8, d{sub calcd} = 1.43 g cm{sup {minus}3}, and space group Pr{sub 1}. The unit cell contains two crystallographically independent molecules that are essentially equivalent with respect to M-M and M-O distances and angles. In each there is a central Mo{sub 4} butterfly with a dihedral angle between the Mo{sub 3} triangles of 132.5{degree}.
- OSTI ID:
- 6946144
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 111:14; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
MOLYBDENUM OXIDES
STRUCTURAL CHEMICAL ANALYSIS
TUNGSTEN OXIDES
ALCOHOLS
CRYSTALLOGRAPHY
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
MEASURING INSTRUMENTS
MEASURING METHODS
NUCLEAR MAGNETIC RESONANCE
CHALCOGENIDES
DATA
HYDROXY COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
MOLYBDENUM COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
RESONANCE
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
400000* - Chemistry
400200 - Inorganic
Organic
& Physical Chemistry
360000 - Materials
360102 - Metals & Alloys- Structure & Phase Studies