Reaction mechanism of silicon-hydrogen bond activation studied using femtosecond to nanosecond IR spectroscopy and Ab initio methods

H. Yang, M. C. Asplund, K. T. Kotz, W. H. Frei, J. Harris, R. Poli, K. M. Smith

Research output: Contribution to journalReview article

Abstract

Photolysis of CpMn(CO)3 in neat Et3SiH at ambient temperatures results in the initial generation of CpMn(CO)2 in two spin states, with differing geometries, selectivities, and rates of reaction. While the apparent rate- determining step for the activation of triethylsilane for singlet CpMn(CO)2 and CpRe(CO)2 is the dissociative rearrangement of the ethyl-bound solvate, triplet CpMn(CO)2 interacts only weakly with the solvent C-H bonds, allowing facile reorientation of Et3SiH until the strongly coupling Si-H bond is encountered. The identities of transient species detected by ultrafast infrared spectroscopy were assigned with the aid of ab initio theoretical methods.

Original languageEnglish (US)
Pages (from-to)346-353
Number of pages8
JournalChemtracts
Volume12
Issue number5
StatePublished - May 1 1999
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry
  • Molecular Biology

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    Yang, H., Asplund, M. C., Kotz, K. T., Frei, W. H., Harris, J., Poli, R., & Smith, K. M. (1999). Reaction mechanism of silicon-hydrogen bond activation studied using femtosecond to nanosecond IR spectroscopy and Ab initio methods. Chemtracts, 12(5), 346-353.