Dependence of activation parameters for phenylchlorocarbene–alkene additions on alkane solvent chain length

Activation energies, enthalpies, and entropies for the addition of phenylchlorocarbene to tetramethylethylene significantly decrease as the reaction solvent lengthens from n-pentane to n-octane to n-decane; additional decreases are minimal in n-pentadecane and n-heptadecane. Electronic structure calculations, employing a continuum solvent model, fail to reproduce the observations; instead, a qualitative model invoking solvent cage effects is proposed.