Interaction of alkanes with unsaturated metal centers. 2. Complexes of alkanes and fluoroalkanes with W(CO) sub 5 in the gas phase

Journal Article · Wed Mar 28 00:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00163a008· OSTI ID:6518531

Brown, C E; Ishikawa, Yoichi; Hackett, P A; Rayner, D M ^[1]

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1. National Research Council Canada, Ottawa, Ontario (Canada)

Time-resolved infrared spectroscopy has been used to study the interaction of a range of open-chain, cyclic, and fluorine-substituted alkanes with the 16-electron species W(CO){sub 5}. W(CO){sub 5} forms reversible complexes with all the unsubstituted alkanes studied except CH{sub 4}. The equilibrium constant K{sub p} = (W(CO){sub 5}L)/((W(CO){sub 5})p(L)), at 300 K, increases with carbon number from 610 {plus minus} 100 atm{sup {minus}1} in cyclohexane. binding energies have also been obtained through temperature studies. They are in the range 7-11 kcal mol{sup {minus}1}, again increasing with the size of the alkanes. In the case of CH{sub 4}, a binding energy K5 kcal mol{sup {minus}1} is implied by their inability to observe a complex. Correlation of the binding energies with C-H {sigma} MO stabilization energies is consistent with a simple molecular orbital picture involving formation of a 2-electron, 3-center C-H-M bond through {sigma} {yields} M electron donation.

• OSTI ID: 6518531
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 112:7; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
INTERACTIONS
METALS
CARBONYLS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
TUNGSTEN COMPOUNDS
DATA
ELEMENTS
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties