Metal alkoxides - models for metal oxides. 9. Hydridoditungsten alkoxides: W/sub 2/(H)(O-i-Pr)/sub 8/Na diglyme and W/sub 2/(H)(I)(OCH/sub 2/-t-Bu)/sub 6/(H/sub 2/NMe). Further investigations of the reaction between W/sub 2/(NMe/sub 2/)/sub 6/(M identical with M) and i-PrOH leading to W/sub 3/(H)/sub 2/(O-i-Pr)/sub 14/
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Reaction between W/sub 2/(NMe/sub 2/)/sub 6/(M identical with M) and i-PrOH (>>6 equiv), which leads to the known compound W/sub 4/(H)/sub 2/(O-i-Pr)/sub 14/, is shown to be critically dependent on the presence of the liberated amine. The addition of i-PrOH (>>6 equiv) to hydrocarbon solutions of W/sub 2/(O-t-Bu)/sub 6/ or W/sub 2/(O-i-Pr)/sub 6/(HNMe/sub 2/)/sub 2/ does not lead to W/sub 4/(H)/sub 2/(O-i-Pr)/sub 14/ but rather yields an oliomeric species (W(O-i-Pr)/sub 3/)/sub n/. From the reaction between W/sub 2/(O-t-Bu)/sub 6/ in hexane/ROH and NaOR (1 equiv), hexane-insoluble compounds are formed: NaW/sub 2/(H)(OR)/sub 8/, where R = i-Pr and CH/sub 2/-t-Bu. Extraction into hexane solution by the addition of diglyme (1 equiv) yields W/sub 2/(H)(O-i-Pr)/sub 8/Na diglyme, which has been characterized by NMR studies and a single-crystal X-ray diffraction study. Crystal data for W/sub 2/(H)(O-i-Pr)/sub 8/Na diglyme at -155 /sup 0/C are the following: a = 24.087 (8) A, b = 16.540 (5) A, c = 12.747 (4) A, ..beta.. = 125.71 (1)/sup 0/, Z = 4,d/sub calcd/ = 1.608 g cm/sup -3/, and space group P2/sub 1//a; for W/sub 2/(H)(I)(OCH/sub 2/-t-Bu)/sub 6/(H/sub 2/NMe) at -158 /sup 0/C a = 18.159 (5) A, b = 10.873 (2) A, c = 11.599 (3) A, ..cap alpha.. = 77.30 (1)/sup 0/, ..beta.. = 109.37 (1)/sup 0/, ..gamma.. = 96.55 (2)/sup 0/, Z = 2,d/sub calcd/ = 1.656 g cm/sup -3/, and space group P1. 31 references, 7 figures, 7 tables.
- Research Organization:
- Indiana Univ., Bloomington
- OSTI ID:
- 6038273
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:2; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Metal alkoxides. Models for metal oxides. 15. Carbon-carbon and carbon-hydrogen bond activation in the reactions between ethylene and ditungsten hexaalkoxides: W sub 2 (OCH sub 2 -t-Bu) sub 6 (. eta. sup 2 -C sub 2 H sub 4 ) sub 2 , W sub 2 (OR) sub 6 (CH sub 2 ) sub 4 (. eta. sup 2 -C sub 2 H sub 4 ), and W sub 2 (OR) sub 6 (. mu. -CCH sub 2 CH sub 2 CH sub 2 ) (where r = CH sub 2 -t-Bu, i-Pr, c-C sub 5 h sub 9 , and c-C sub 6 H sub 11 ). Preparations, properties, structures, and reaction mechanisms
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Related Subjects
01 COAL, LIGNITE, AND PEAT
010403 -- Coal & Coal Products-- Hydrogenation-- (-1987)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
EXPERIMENTAL DATA
INFORMATION
LENGTH
LIGANDS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
RESONANCE
SCATTERING
SPACE GROUPS
SPECTRA
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION
010403 -- Coal & Coal Products-- Hydrogenation-- (-1987)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
EXPERIMENTAL DATA
INFORMATION
LENGTH
LIGANDS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
RESONANCE
SCATTERING
SPACE GROUPS
SPECTRA
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION