Abstract
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 language | English (US) |
---|---|
Pages (from-to) | 183-192 |
Number of pages | 10 |
Journal | Journal of Organometallic Chemistry |
Volume | 596 |
Issue number | 1-2 |
DOIs | |
State | Published - Feb 29 2000 |
Externally published | Yes |
All Science Journal Classification (ASJC) codes
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry
Keywords
- Dissociative mechanism
- Dynamics
- Group 6
- IR spectroscopy
- Ultrafast spectroscopy