Tracking "invisible" alkylchlorocarbenes by their sigma --> p absorptions: dynamics and solvent interactions.
Contrary to implications in the literature, the sigma --> p absorptions of alkylchlorocarbenes (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 MeCCl and PhCH2CCl 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.
Moss
Robert A
RA
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ 08903, USA. moss@rutchem.rutgers.edu
Tian
Jingzhi
J
Sauers
Ronald R
RR
Krogh-Jespersen
Karsten
K