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Metallophosphorus clusters: Ru/sub 5/(CO)/sub 12/(. mu. 4PPh)(. mu. /sub 3/-CCH/sub 2/-i-Pr)(. mu. /sub 2/-PPh/sub 2/) and HRu/sub 5/ (CO)/sub 10/(. mu. /sub 4/-PPh)/sub 2/(. mu. /sub 3/-PPh)(. mu. /sub 2/PPh/sub 2/), face-capped-octahedral and pentagonal-bipyramidal clusters via stepwise reduction of an acetylide

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00328a067· OSTI ID:6167604
; ;
The results of studies of the photocatalytic hydrogenation of ethylene by Fe(CO/sub 3/(C/sub 2/H/sub 4/) for the very efficient preparation of ethane are reported. These suggest that the mechanism of the reaction employing the Fe(CO)/sub 3/(C/sub 2/H/sub 4/) is different from that employing just Fe(CO)/sub x/. In an attempt to explain the reaction mechanism, four processes considered to occur with the advent of each laser pulse were: 1) photo-ejection of CO from precatalyst with unit quantum efficiency to create active catalyst; 2) adsorption of light by catalyst remaining from previous pulses; 3) catalyst recombination with CO; and 4) catalyst-promoted hydrogenation of ethylene. From consideration of these processes, a mathematical model is developed that suggests that the recombination in the case of a substituted carbonyl, Fe(CO)/sub 3/(C/sub 2/H/sub 4/), is slowed by an activation barrier, possibly associated with a required rearrangement of the ethylene ligand.
Research Organization:
Univ. of Waterloo, Ontario
OSTI ID:
6167604
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:16; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

090121* -- Hydrocarbon Fuels-- Chemical Synthesis-- (1976-1989)
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
ALKANES
ALKENES
CARBONYLS
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
ETHANE
ETHYLENE
HYDROCARBONS
HYDROGENATION
KINETICS
MATHEMATICAL MODELS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
REACTION KINETICS
SYNTHESIS