Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Gas-phase organometallic catalysis: kinetics and mechanisms of the hydrogenation of ethylene by Fe(CO)/sub 3/(C/sub 2/H/sub 4/)/sub 2/

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00260a004· OSTI ID:7148115
;

Inert homogeneous gas-phase mixtures of ethylene and hydrogen plus a catalytic amount of Fe(CO)/sub 5/ are transformed into active ethylene hydrogenation systems upon irradiation by near-UV light from a pulsed nitrogen laser. Organometallic species present in the active catalytic mixture are identified and monitored by Fourier transform infrared spectroscopy. The catalyzed reaction is followed by gas chromatography, which provides a measure of ethylene and hydrogenated product concentrations. The catalytic process is efficient in its use of light, with typical room temperature quantum yields (product ethane molecules formed per photon absorbed) of 20 or more. The absorbed laser light generates a reservoir of Fe(CO)/sub 3/(C/sub 2/H/sub 4/)/sub 2/, which thermally dissociates by losing one highly labile ethylene to yield the active catalyst, Fe(CO)/sub 3/(C/sub 2/H/sub 4/). When the photolysis light is removed, catalytic activity is observed to decline as the catalyst combines with free CO to form stable Fe(CO)/sub 4/(C/sub 2/H/sub 4/). The rate of organic product formation is directly proportional to the catalysts reservoir concentration. Quantum efficiency of ethane production and the rate of Fe(CO)/sub 3/(C/sub 2/H/sub 4/)/sub 2/ decay are studied as functions of ethylene, hydrogen, CO and Fe(CO)/sub 5/ pressures. The results provide information on the mechanism of catalysis, as well as elementary rate parameters for many of the organometallic reactions.

Research Organization:
Purdue Univ., West Lafayette, IN (USA)
OSTI ID:
7148115
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:26; ISSN JACSA
Country of Publication:
United States
Language:
English

Similar Records

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 · Wed Aug 08 00:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States) · OSTI ID:6167604
Metal cluster catalysis. Kinetics and mechanism of the catalytic hydrogenation of ethylene by the ruthenium cluster complex H/sub 4/Ru/sub 4/(CO)/sub 12/
Journal Article · Thu Jul 01 00:00:00 EDT 1982 · Inorg. Chem.; (United States) · OSTI ID:6876659
Mechanism of hydrogenation of ethylene via photoproduced unsaturated iron carbonyl in the gas phase
Journal Article · Wed Jan 23 23:00:00 EST 1991 · Journal of Physical Chemistry; (USA) · OSTI ID:5887134

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKENES
CARBONYLS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
EFFICIENCY
ETHYLENE
EXPERIMENTAL DATA
FLUIDS
GAS LASERS
GASES
HYDROCARBONS
INFORMATION
IRON COMPOUNDS
KINETICS
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PULSE TECHNIQUES
QUANTITY RATIO
QUANTUM EFFICIENCY
REACTION KINETICS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS