ORGN 451 |
| Contrary to implications in the literature, the sigma to p absorptions of alkychlorocarbenes (RCCl) are readily acquired by laser flash photolysis with UV-vis detection in solution at ambient temperature. Examples include RCCl with R = methyl, benzyl, t-butyl, 1-adamantyl, and cyclopropyl. These absorptions permit direct monitoring of carbene reactions and the formation of carbene-solvent complexes. The kinetics of the reactions of ‘free' and complexed methylchlorocarbene and benzylchlorocarbene were directly followed with tetramethylethylene and 1-hexene. Particularly effective complexation was provided by anisole and 1,3-dimethoxybenzene, which modulated the rates of intermolecular carbene additions. Computational studies are presented which aid in understanding the carbene absorption spectra and the nature of the solvent complexes. |
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High Energy Species
1:00 PM-4:40 PM, Tuesday, August 21, 2007 BCEC -- 254 A/B, Oral
Division of Organic Chemistry |