Tungsten alkoxides of the W(OR)/sub 6/ series
A method for the synthesis of W(CR)/sub 6/ (R = Me, Et, n-Bu) (I) with the aid of an exchange reaction between a suspension of WCl/sub 6/ in ether or hexane with an alcoholic solution of NaOH at O/sup 0/C with 15-25% yields has been proposed. The reaction of WC1/sub 6/ with LiOBu-t gives WO(OBu-t)/sub 4/, apparently as a consequence of the impossibility of the existence of six such highly branched ligands as t-BuO in the coordination sphere of W(VI). The synthesis of compounds of type I by the successive alkoxylation of WC1/sub 6/ by esters of silicic acid and NaOR is restricted to W(OMe)/sub 6/ alone. The reaction of WC1/sub 6/ with Si (OEt)/sub 4/ gives WO(OEt)/sub 2/C1/sub 2/ (II) and W(OEt)/sub 4/C1/sub 2/ (III), which has not previously been described. Compound II, unlike III, is resistant to reduction and forms WO(OEt)/sub 4/ with a quantitative yield when it is reacted with NaOR. Compound III was obtained in the form of yellowish green crystals with T/sub um/ = 29 to 31/sup 0/C, which are soluble in ethanol and hydrocarbons. In the case of the exchange reaction of WC1/sub 6/ with n-BuOH and NH/sub 3/, WO(OBu-n)/sub 4/ forms instead of WO(OBu-n)/sub 6/, whose formation was indicated in the literature. The compound W(OMe)/sub 6/ crystallizes with a hexagonal structure having the parameters a = 7.12 and c = 6.64 'angstcom'. The IR and mass spectra of compounds I and III have been presented.
- Research Organization:
- M.V. Lomonosov Moscow State Univ.
- OSTI ID:
- 6367199
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 11:12; ISSN SJCCD
- Country of Publication:
- United States
- Language:
- English
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ALKOXIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
COMPLEXOMETRY
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALLIZATION
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
HEXAGONAL LATTICES
INFRARED SPECTRA
KINETICS
LATTICE PARAMETERS
LIGANDS
MASS SPECTRA
PHASE TRANSFORMATIONS
REACTION KINETICS
REDOX POTENTIAL
REFRACTORY METAL COMPOUNDS
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN CHLORIDES
TUNGSTEN COMPLEXES
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION
YIELDS