Photochemistry of Fe(CO)/sub 4/ adsorbed onto porous vycor glass

Journal Article · Wed May 27 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00245a016· OSTI ID:6508871

Darsillo, M S; Gafney, H D; Paquette, M S

Fe(CO)/sub 5/ physisorbs onto porous Vycor glass without disruption of its primary coordination sphere. The spectral properties of the adsorbed complex mirror those found in fluid solution, and UV photolysis in vacuo leads to formation of the tetracarbonyl with a quantum yield of unity. The tetracarbonyl rapidly reacts with the PVG surface and chemisorbed water to form the spectrally distinct, oxidative addition products H-Fe(CO)/sub 4/-OSi and H-Fe(CO)/sub 4/-OH. These undergo secondary photolysis to form, depending on the initial loading, either elemental iron or the trimeric cluster Fe/sub 3/(CO)/sub 12/. Diffuse reflectance FTIR spectra, recorded after CW or pulsed laser excitation, establish the presence of dimeric and trimeric intermediates. Trapping experiments with CO and trimethylphosphine indicate a photochemically driven, stepwise reaction sequence in which the so-called mobile intermediate, principally Fe(CO)/sub 3/, reacts with H-Fe(CO)/sub 4/-OH and Fe(CO)/sub 5/(ads) to form dimeric and trimeric products.

• Research Organization: City Univ. of New York, Flushing, NY
• OSTI ID: 6508871
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ADSORPTION
CARBONYLS
CHEMICAL REACTIONS
CHEMISTRY
DATA
EFFICIENCY
EXPERIMENTAL DATA
GLASS
INFORMATION
IRON COMPOUNDS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
QUANTUM EFFICIENCY
REACTION INTERMEDIATES
SORPTION
SORPTIVE PROPERTIES
SURFACE PROPERTIES
TRANSITION ELEMENT COMPOUNDS
VYCOR