Laser Flash Photolysis Studies of the Reaction of Arylhalocarbenes with Tetramethylethylene as a Function of Solvent

Absolute rate constants of reaction of chlorophenylcarbene, bromophenylcarbene, and chloro- p -nitrophenylcarbene with tetramethylethylene (TME; k TME ) are similar in alkane solvent, Freon-113, benzene, tetrahydrofuran, and acetonitrile. Solvation of the carbenes has little influence on k TME . Strong specific solvation which impedes cycloaddition reactions of the arylhalocarbenes with TME is not found with these carbenes, but the existence of weakly bound complexes with spectra and kinetics similar to those of free carbenes cannot be ruled out.