Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons

Matthew C. Asplund, Preston T. Snee, Jake S. Yeston, Matthew J. Wilkens, Christine K. Payne, Haw Yang, Kenneth T. Kotz, Heinz Frei, Robert G. Bergman, Charles B. Harris

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51 Scopus citations

Abstract

The photochemical C-H activation reactions of η3-Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)2 (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)2 molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η3-Tp*Rh(CO)2 studies.

Original languageEnglish (US)
Pages (from-to)10605-10612
Number of pages8
JournalJournal of the American Chemical Society
Volume124
Issue number35
DOIs
StatePublished - Sep 4 2002
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Asplund, M. C., Snee, P. T., Yeston, J. S., Wilkens, M. J., Payne, C. K., Yang, H., Kotz, K. T., Frei, H., Bergman, R. G., & Harris, C. B. (2002). Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons. Journal of the American Chemical Society, 124(35), 10605-10612. https://doi.org/10.1021/ja020418s