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
- Indiana Univ., Bloomington (USA)
W{sub 2}(OR){sub 6} (M {triple bond}M) compounds and ethylene (1 atm, 22{degree}C) react in alkane and aromatic hydrocarbon solvents to give W{sub 2}(OR){sub 6}({mu}-CCH{sub 2}CH{sub 2}CH{sub 2}) compounds and ethane, where R = i-Pr, c-C{sub 5}H{sub 9}, c-C{sub 6}H{sub 11}, and CH{sub 2}-t-Bu. Under comparable conditions, W{sub 2}(O-t-Bu){sub 6} and ethylene fail to react. In the formation of W{sub 2}(OR){sub 6}({mu}-CCH{sub 2}CH{sub 2}CH{sub 2}) compounds, the intermediates W{sub 2}(OCH{sub 2}-t-Bu){sub 6}({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} and W{sub 2}(OR){sub 6}(CH{sub 2}){sub 4}({eta}{sup 2}-C{sub 2}H{sub 4}), where R = C-C{sub 5}H{sub 9}, i-Pr, and CH{sub 2}-t-Bu, have been characterized. For R = i-Pr and CH{sub 2}-t-Bu, the intermediates are shown to be formed reversibly from W{sub 2}(OR){sub 6} and ethylene. The compound W{sub 2}(O-i-Pr){sub 6}(CH{sub 2}){sub 4}({eta}{sup 2}-C{sub 2}H{sub 4}) has been fully characterized by an X-ray study and found to contain a metallacyclopentane ring and a W-{eta}{sup 2}-C{sub 2}H{sub 4} moiety, one at each metal center. The pyridine adduct W{sub 2}(O-i-Pr){sub 6}({mu}-CCH{sub 2}CH{sub 2}ch{sub 2})(py) has been fully characterized and shown to contain a novel 1,6-dimetallabicyclo(3.1.0)hex-1(5)-ene organometallic core. All compounds have been characterized by {sup 13}C and {sup 1}H NMR studies. Various aspects of the reaction pathway have been probed by the use of isotopically labeled ethylenes, and a proposed general scheme is compared to previous studies of ethylene activation at mononuclear metal centers and carbonyl dinuclear and cluster compounds.
- OSTI ID:
- 6946164
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:14; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360000 -- Materials
360102 -- Metals & Alloys-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400000* -- Chemistry
400200 -- Inorganic
Organic
& Physical Chemistry
ALKENES
BONDING
CHALCOGENIDES
CHEMICAL PROPERTIES
CRYSTALLOGRAPHY
DATA
DATA ANALYSIS
ETHYLENE
EXPERIMENTAL DATA
FABRICATION
HYDROCARBONS
INFORMATION
JOINING
MAGNETIC RESONANCE
MEASURING INSTRUMENTS
MEASURING METHODS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
RESONANCE
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
TUNGSTEN OXIDES