Characterization of transient species and products in photochemical reactions of Re(dmb)(CO)3 et with and without CO2

Kazuteru Shinozaki, Yukiko Hayashi, Bruce S. Brunschwig, Etsuko Fujita

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10 Citations (Scopus)

Abstract

Transient FT-IR spectra of fac-Re(dmb)(CO)3(Et) after laser excitation (355 nm) were investigated in THF under Ar and CO2 atmospheres. The CO stretching bands of Re(dmb)(CO) 3(THF) grow (2008 and 1897 cm-1) and those of Re(dmb)(CO)3(Et) bleach (1987 and 1875 cm-1) at times <1 μs, consistent with clean cleavage of the Re-Et bond. Under a CO 2 atmosphere, the long-lived radical (τ > 100 ms) converts slowly to the formato complex, Re(dmb)(CO)3(OC(O)H) (2020, 1916, 1873 and 1630 cm-1). When the solvent is slightly wet, the bicarbonate complex, Re(dmb)(CO)3(OC(O)OH), is also observed after photolysis under CO2.

Original languageEnglish
Pages (from-to)27-36
Number of pages10
JournalResearch on Chemical Intermediates
Volume33
Issue number1-2
DOIs
Publication statusPublished - Jan 1 2007

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Keywords

  • CO
  • FT-IR
  • Laser excitation
  • Re(dmb)(CO)(Et)

ASJC Scopus subject areas

  • Chemistry(all)

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