New insights into the photochemistry of [CpFe(CO)2]2 using picosecond through microsecond time-resolved infrared spectroscopy (TRIR)

Christopher M. Brookes, Justin P. Lomont, Son C. Nguyen, James A. Calladine, Xue Zhong Sun, Charles B. Harris, Michael W. George

Research output: Journal PublicationArticlepeer-review

5 Citations (Scopus)

Abstract

Picosecond to microsecond time-resolved infrared spectroscopy (TRIR) has been used to investigate the photochemistry of [CpFe(CO)2] 2. The early-time TRIR spectra are dominated by vibrationally hot transient species and this leads to spectra with broad featureless bands. The majority (84%) of the well characterized Cp2Fe2(μ-CO) 3, with a band at 1824 cm-1, grows in on a timescale (15-20 ps) similar to the cooling rate of many of the ν(CO) bands, and this arises from presumably the initially formed species, [CpFe(CO)(μ-CO) 2FeCp] of which we were unable to find clear evidence. However, Cp2Fe2(μ-CO)3 is formed by two different processes and under CO the remaining slower formation (16%) occurs at the same rate (46 ± 2 ns) as a transient band at 1908 cm-1 decays. The 1908 cm-1 had been previously observed in an earlier study but its identity remained unclear. We find that this 1908 cm-1 intermediate has no corresponding bridging ν(CO) band and is formed by a 1-photon process. This band is assigned to a dicarbonyl-loss photoproduct, [CpFe(CO)]2 and is a rare example of double CO loss occurring following a single-photon excitation in the condensed phase.

Original languageEnglish
Pages (from-to)130-134
Number of pages5
JournalPolyhedron
Volume72
DOIs
Publication statusPublished - 18 Apr 2014
Externally publishedYes

Keywords

  • Infrared spectroscopy
  • Iron carbonyls
  • Photochemistry
  • Time-resolved spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Fingerprint

Dive into the research topics of 'New insights into the photochemistry of [CpFe(CO)2]2 using picosecond through microsecond time-resolved infrared spectroscopy (TRIR)'. Together they form a unique fingerprint.

Cite this