Photoinduced β-Hydrogen Elimination and Radical Formation with CpW(CO)3(CH2CH3): Ultrafast IR and DFT Studies
| Autor: | Charles B. Harris, and T. Don Tilley, Elizabeth A. Glascoe, Jennifer E. Shanoski, Christine K. Payne, Benjamin V. Mork, Robert A. DiStasio, Matthias F. Kling |
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| Rok vydání: | 2007 |
| Předmět: | |
| Zdroj: | Organometallics. 26:1424-1432 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | The initial steps of β-hydrogen elimination from the complex CpW(CO)3(CH2CH3) were studied using ultrafast infrared and step-scan FTIR spectroscopy combined with density functional theory calculations. The reaction was initiated by a pulse of UV light at 266 nm and followed with infrared light on the femto- to microsecond timescale, allowing for the identification and kinetic characterization of transients. In the process of β-H elimination, the primary photoproduct was found to be an α-H stabilized complex and the dynamics of the elusive species cis-CpW(CO)3(H)(CH2CH2) were resolved, allowing for a full kinetic and thermodynamic analysis of the reaction. In a side reaction, CpW(CO)3• is formed via ethyl ligand dissociation; the measured formation rate indicates that the complex forms from a vibrationally excited parent complex. Density functional theory calculations of all relevant transient intermediates and transition states involved in β-H elimination of CpW(CO)3(CH2CH3) are presented. These calculati... |
| Databáze: | OpenAIRE |
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