Tracking “Invisible” Alkylchlorocarbenes by Their σ → p Absorptions:  Dynamics and Solvent Interactions

Tracking “Invisible” Alkylchlorocarbenes by Their σ → p Absorptions:  Dynamics and Solvent Interactions

Contrary to implications in the literature, the σ → 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 absorpt...

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Veröffentlicht in:Journal of the American Chemical Society 2007-08, Vol.129 (32), p.10019-10028
Hauptverfasser: Moss, Robert A, Tian, Jingzhi, Sauers, Ronald R, Krogh-Jespersen, Karsten
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container_end_page 10028
container_issue 32
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container_title Journal of the American Chemical Society
container_volume 129
creator Moss, Robert A
Tian, Jingzhi
Sauers, Ronald R
Krogh-Jespersen, Karsten
description Contrary to implications in the literature, the σ → 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.
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title Tracking “Invisible” Alkylchlorocarbenes by Their σ → p Absorptions:  Dynamics and Solvent Interactions
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