Carbon-hydrogen bond activation and carbon-carbon bond formation in the reaction between ethylene and hexaisopropoxyditungsten

Journal Article · Wed Sep 16 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00253a061· OSTI ID:5890716

Chisholm, M H; Hampden-Smith, M

Ethylene reacts with certain metal surfaces to give a capping (..mu../sub 3/) ethylidyne ligand. In triosmium carbonyl chemistry ethylene has been shown to undergo successive C-H activation to give a ..mu..-sigma,..pi..-vinyl and a ..mu..-vinylidene ligand. A similar reaction sequence has been reported by Puddephatt and co-workers in the addition of ethyne to a hydrido triangulo platinum complex. The authors have repeatedly emphasized the relationships, both structural and chemical, between reduced metal oxides of molybdenum and tungsten and smaller alkoxide clusters and their larger (closo) counterparts. For example, the square-Mo/sub 4/Cl/sub 4/(O-i-Pr)/sub 4/ and butterfly-Mo/sub 4/Br/sub 4/(O-i-Pr)/sub 2/ molecules are arachno subunits of the M/sub 6/(..mu../sub 3/-X)/sub 8/ cluster unit, and W/sub 4/(O-i-Pr)/sub 12/ represents a fragment of the M/sub 6/(..mu../sub 2/-X)/sub 12/ unit. Furthermore the M/sub 4/-alkoxide clusters are formed from the coupling of M/sub 2/ alkoxides by steric control in the choice of the OR group. Indeed the authors have established that an equilibrium exists between W/sub 4/(O-i-Pr)/sub 12/ and W/sub 2/(O-i-Pr)/sub 6/. One of the authors hypotheses is that these small unsaturated alkoxide cluster units may provide models for active sites on reduced metal oxide surfaces. They describe here the observation of the activation of ethylene by W/sub 2/(O-i-Pr)/sub 6/ under extremely mild conditions.

• Research Organization: Indiana Univ., Bloomington
• OSTI ID: 5890716
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
ALKENES
CARBON
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
ENERGY
ETHYLENE
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN
INFORMATION
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES