Femtosecond infrared studies of ligand rearrangement reactions: Silyl hydride products from Group 6 carbonyls

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

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36 Scopus citations


The ultrafast dynamics of the Si-H bond activation reaction by the Group 6 d6 organometallic compounds M(CO)5 (M = Cr, Mo, and W) have been studied in neat tri-substituted silanes under ambient conditions. The ultrafast spectral evolutions of the CO stretching bands were monitored following UV photolysis using femtosecond pump-probe spectroscopic methods. It was found that the coordinatively unsaturated species, which is formed following CO photolysis from the parent molecule, is quickly solvated ( < 2 ps) via the C-H bonds of the solvent. These species then rearranged to the silyl hydride product on a timescale of a few nanoseconds. These results were augmented by rearrangement studies in neat ethanol, propanol and hexanol solutions in which the initially formed metal C-H complex rearranged to the metal hydroxyl complex. The mechanism of this rearrangement was discussed by comparison of the data with various models in the literature. It was found that a mechanism that is primarily dissociative in nature provided the best description of the experimental data.

Original languageEnglish (US)
Pages (from-to)183-192
Number of pages10
JournalJournal of Organometallic Chemistry
Issue number1-2
StatePublished - Feb 29 2000
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


  • Dissociative mechanism
  • Dynamics
  • Group 6
  • IR spectroscopy
  • Ultrafast spectroscopy


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