Triplet organometallic reactivity under ambient conditions: An ultrafast UV pump/IR probe study

P. T. Snee, C. K. Payn, K. T. Kotz, H. Yang, C. B. Harris

Research output: Contribution to journalArticlepeer-review

81 Scopus citations

Abstract

The reactivity of triplet 16-electron organometallic species has been studied in room-temperature solution using femtosecond UV pump IR probe spectroscopy. Specifically, the Si-H bond-activation reaction of photogenerated triplet Fe(CO)4 and triplet CpCo(CO) with triethylsilane has been characterized and compared to the known singlet species CpRh(CO). The intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical calculations. The triplet organometallics have a greater overall reactivity than singlet species due to a change in the Si-H activation mechanism, which is due to the fact that triplet intermediates coordinate weakly at best with the ethyl groups of triethylsilane. Consequently, the triplet species do not become trapped in alkyl-solvated intermediate states. The experimental results are compared to the theoretical calculations, which qualitatively reproduce the trends in the data.

Original languageEnglish (US)
Pages (from-to)2255-2264
Number of pages10
JournalJournal of the American Chemical Society
Volume123
Issue number10
DOIs
StatePublished - Oct 9 2001
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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