Spectroscopic characterization of intermediates in CO2 reduction with rhenium photocatalysts

Etsuko Fujita, Yukiko Hayashi, Shouichi Kita, Bruce S. Brunschwig

Research output: Contribution to journalArticle

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Abstract

We are investigating fundamental processes for the efficient capture and chemical conversion of solar energy using transition metal complexes. Mechanistic and kinetic knowledge of photo-induced multi-electron transfer reactions and bond forming (and/or breaking) reactions is crucial to understanding photochemical activation of CO2 and to the design of more efficient photoconversion systems. We have investigated the excited state properties and the reactivities of the photochemically produced species of fac-Re(dmb)(CO)3X (where dmb = 4,4′-dimethyl-2,2′- bipyridine, X = halide or solvent) by transient UV-vis, transient FTIR, and NMR spectroscopy. The reduced monomer, Re(dmb)(CO)3S (S = solvent) dimerizes (kd = 40 M-1 S-1) sreversibly in THF. The reaction of Re(dmb)(CO)3S with CO2 is very slow (kCO2 <0.1 M-1 s-1) and liberates CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO) 3(dmb)Re-CO(O)-Re(dmb)(CO)3, is identified as a key intermediate in the CO formation. [Re(dmb)(CO)3]2(OCO 2), Re(dmb)(CO)3(OC(O)OH) and [Re(dmb)(CO) 3S]+ were detected as oxidation products by means of NMR, IR, and FAB MS.

Original languageEnglish
Pages (from-to)271-276
Number of pages6
JournalStudies in Surface Science and Catalysis
Volume153
Publication statusPublished - 2004

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Rhenium
rhenium
Carbon Monoxide
Photocatalysts
Metal complexes
Excited states
Dimers
Solar energy
Nuclear magnetic resonance spectroscopy
Transition metals
nuclear magnetic resonance
FORTRAN
Monomers
Chemical activation
Nuclear magnetic resonance
solar energy
Oxidation
Kinetics
halides
Electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

Spectroscopic characterization of intermediates in CO2 reduction with rhenium photocatalysts. / Fujita, Etsuko; Hayashi, Yukiko; Kita, Shouichi; Brunschwig, Bruce S.

In: Studies in Surface Science and Catalysis, Vol. 153, 2004, p. 271-276.

Research output: Contribution to journalArticle

Fujita, Etsuko ; Hayashi, Yukiko ; Kita, Shouichi ; Brunschwig, Bruce S. / Spectroscopic characterization of intermediates in CO2 reduction with rhenium photocatalysts. In: Studies in Surface Science and Catalysis. 2004 ; Vol. 153. pp. 271-276.
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