Tungsten alkoxides of the WO(OR)/sub 4/ series
The compounds WO(OR)/sub 4/ (I) (where R = Me, Et, i-Pr, n-Bu) have been synthesized with quantitative yields by reacting ethereal solutions of WOCl/sub 4/ with alcoholic solutions of NaOR at 0/sup 0/C. It has been established that the method for the synthesis of I described in the literature, which involves the preliminary alcoholysis of WOCl/sub 4/, results in the contamination of I by hydrolysis products, i.e., WO/sub 2/(OR)/sub 2/. The solubility polytherm of WO(OEt)/sub 4/ in EtOH has been studied up to the melting point of the alkoxide (126/sup 0/C). It has been established mass-spectrometrically that the transition to the gaseous phase is accompanied by the disproportionation of WO(OR)/sub 4/ to W(OR)/sub 6/ and WO/sub 2/(OR)/sub 2/, whose presence was also discovered in the x-ray diffraction analysis of the sublimation products of WO(OMe)/sub 4/. The compound WO(OBu-t)/sub 4/ sublimes without decomposition. Similarity between the structures of the methoxide and the ethoxide and that of WOCl/sub 4/ (the positioning of (trans-WO/sub 2/L/sub 4/) octahedrons at the vertices and center of a tetragonal cell) has been established on the basis of x-ray powder diffraction investigations. The IR-spectroscopic data confirm the existence in structure I of O dot-dot-dot/single bond W-O bridges (the absorption bands at 800 and 600 cm/sup -1/ correspond to two types of bonds, viz, dot-dot-dot/single bond W-O dot-dot-dot/single bond W and W-OR) and mono- or oligomeric WO(OBu-t)/sub 4/ molecules (the band at 950 cm/sup -1/ corresponds to terminal W=O bonds). The diffuse reflectance spectra in the 40,000-4000-cm/sup -1/ region have been presented.
- Research Organization:
- Lomonosov Moscow State Univ., Moscow (Russian Federation)
- OSTI ID:
- 6413735
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Vol. 11:11; Other Information: Translated from Koordinatsionnaya Khimiya; 11: No.11, 1521-1528(Nov 1985)
- Country of Publication:
- United States
- Language:
- English
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Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/
Bimetallic alkoxides of tungsten (VI)
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
ALKOXIDES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TUNGSTEN COMPLEXES
CARBON 12
CATALYTIC EFFECTS
CHEMICAL BONDS
COMPLEXOMETRY
INFRARED SPECTRA
IONIZATION POTENTIAL
MASS SPECTRA
MELTING POINTS
ORGANIC SOLVENTS
OXIDATION
OXYCHLORIDES
PHASE STUDIES
REDOX POTENTIAL
REDUCTION
SOLUBILITY
SUBLIMATION
TETRAGONAL LATTICES
TUNGSTEN 182
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION
CARBON ISOTOPES
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
EVAPORATION
EVEN-EVEN NUCLEI
HALOGEN COMPOUNDS
HEAVY NUCLEI
ISOTOPES
LIGHT NUCLEI
NUCLEI
OXYGEN COMPOUNDS
PHASE TRANSFORMATIONS
PHYSICAL PROPERTIES
REFRACTORY METAL COMPOUNDS
SCATTERING
SOLVENTS
SPECTRA
STABLE ISOTOPES
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TRANSITION TEMPERATURE
TUNGSTEN ISOTOPES
400201* - Chemical & Physicochemical Properties
360602 - Other Materials- Structure & Phase Studies