Cookies on this website

We use cookies to ensure that we give you the best experience on our website. If you click 'Accept all cookies' we'll assume that you are happy to receive all cookies and you won't see this message again. If you click 'Reject all non-essential cookies' only necessary cookies providing core functionality such as security, network management, and accessibility will be enabled. Click 'Find out more' for information on how to change your cookie settings.

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 ((3)4) 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, (3)4 decays to form (1)4 x 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 (1)4 x L. The conversion of (3)4 to (1)4 x L has been monitored directly for the first time (L = heptane, kobs = 7.8(+/- 0.3) x 10(7) s(-1); scCH4, 5(+/- 1) x 10(6) s(-1); scXe, 2.1(+/- 0.1) x 10(7) s(-1)). In scAr, (3)4 and 3 react with CO to form 5 and (3)4, respectively. We have determined the rate constant (kCO = 1.2 x 10(7) dm3 mol(-1) s(-1)) for the reaction of (3)4 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 (3)4 reacting with Xe or CH4 to form (1)4 x Xe or (1)4 x CH4. The relative yield, [(3)4]:[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 publication





Journal of the American Chemical Society

Publication Date





10713 - 10720


School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.