Aryldichloromethide carbanions

Rate constants have been measured for the capture of para-substituted phenylchloro-carbenes by chloride ions to form aryldichloromethide carbanions and for the additions of these carbanions to acrylonitrile.144 A conventional interpretation of the Hammett correlations has suggested that the reactions of carbenes with Cl- traverse early transition states. 

Substituted arylchlorocarbenes reacted reversibly with chloride anion in dichloroethane to form the corresponding aryldichloromethide carbanions. Equilibrium constants and rate constants for the forward and reverse reactions were correlated by the Hammett equation. DFT (density functional theory) methods were used to compute equilibrium constants and electronic absorption spectra. 

A study of the reactions of aryldichloromethide carbanions [22] is presented here to illustrate the use of the Hammett equation in exploring mechanistic investigations. For the reaction in Equation 4.54, the disappearance of the initially formed carbene is followed by UV spectroscopy... 

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See also in sourсe #XX -- [ ]

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