Unraveling the photochemistry of Fe(CO)5 in solution

Observation of Fe(CO)3 and the conversion between 3Fe(CO)4 and 1Fe(CO)4(solvent)

Peter Portius, Jixin Yang, Xue Zhong Sun, David Grills, Pavel Matousek, Anthony W. Parker, Michael Towrie, Michael W. George

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

The photochemistry of Fe(CO)5 (5) has been studied in heptane, supercritical (sc) Ar, scXe, and scCH4 using time-resolved infrared spectroscopy (TRIR). 3Fe(CO)4 (34) and Fe(CO)3(solvent) (3) are formed as primary photoproducts within the first few picoseconds. Complex 3 is formed via a single-photon process. In heptane, scCH4, and scXe, 34 decays to form 14·L (L = heptane, CH4, or Xe) as well as reacting with 5 to form Fe2(CO)9. In heptane, 3 reacts with CO to form 14·L. The conversion of 34 to 14·L has been monitored directly for the first time (L = heptane, kobs = 7.8(±0.3) x 107 s-1; scCH4, 5(±1) x 106 s-1; scXe, 2.1(±O.1) x 107 s-1). In scAr, 34 and 3 react with CO to form 5 and 34, respectively. We have determined the rate constant (kCO = 1.2 x 107 dm3 mol -1 s-1) for the reaction of 34 with CO in scAr, and this is very similar to the value obtained previously in the gas phase. Doping the scAr with either Xe or CH4 resulted in 34 reacting with Xe or CH4 to form 14·Xe or 14·CH4. The relative yield, [34]:[3] decreases in the order heptane > scXe > scCH4 ≫ scAr, and pressure-dependent measurements in scAr and scCH4 indicate an influence of the solvent density on this ratio.

Original languageEnglish
Pages (from-to)10713-10720
Number of pages8
JournalJournal of the American Chemical Society
Volume126
Issue number34
DOIs
Publication statusPublished - Sep 1 2004

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Photochemistry
Heptanes
Photochemical reactions
Heptane
Carbon Monoxide
Cicatrix
Observation
L Forms
Photons
iron pentacarbonyl
Infrared spectroscopy
Rate constants
Spectrum Analysis
Gases
Doping (additives)
Pressure

ASJC Scopus subject areas

  • Chemistry(all)

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Unraveling the photochemistry of Fe(CO)5 in solution : Observation of Fe(CO)3 and the conversion between 3Fe(CO)4 and 1Fe(CO)4(solvent). / Portius, Peter; Yang, Jixin; Sun, Xue Zhong; Grills, David; Matousek, Pavel; Parker, Anthony W.; Towrie, Michael; George, Michael W.

In: Journal of the American Chemical Society, Vol. 126, No. 34, 01.09.2004, p. 10713-10720.

Research output: Contribution to journalArticle

Portius, Peter ; Yang, Jixin ; Sun, Xue Zhong ; Grills, David ; Matousek, Pavel ; Parker, Anthony W. ; Towrie, Michael ; George, Michael W. / Unraveling the photochemistry of Fe(CO)5 in solution : Observation of Fe(CO)3 and the conversion between 3Fe(CO)4 and 1Fe(CO)4(solvent). In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 34. pp. 10713-10720.
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abstract = "The photochemistry of Fe(CO)5 (5) has been studied in heptane, supercritical (sc) Ar, scXe, and scCH4 using time-resolved infrared spectroscopy (TRIR). 3Fe(CO)4 (34) and Fe(CO)3(solvent) (3) are formed as primary photoproducts within the first few picoseconds. Complex 3 is formed via a single-photon process. In heptane, scCH4, and scXe, 34 decays to form 14·L (L = heptane, CH4, or Xe) as well as reacting with 5 to form Fe2(CO)9. In heptane, 3 reacts with CO to form 14·L. The conversion of 34 to 14·L has been monitored directly for the first time (L = heptane, kobs = 7.8(±0.3) x 107 s-1; scCH4, 5(±1) x 106 s-1; scXe, 2.1(±O.1) x 107 s-1). In scAr, 34 and 3 react with CO to form 5 and 34, respectively. We have determined the rate constant (kCO = 1.2 x 107 dm3 mol -1 s-1) for the reaction of 34 with CO in scAr, and this is very similar to the value obtained previously in the gas phase. Doping the scAr with either Xe or CH4 resulted in 34 reacting with Xe or CH4 to form 14·Xe or 14·CH4. The relative yield, [34]:[3] decreases in the order heptane > scXe > scCH4 ≫ scAr, and pressure-dependent measurements in scAr and scCH4 indicate an influence of the solvent density on this ratio.",
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AU - Towrie, Michael

AU - George, Michael W.

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