Evidence for molecular complexes in the mechanism of additions of iodine mono-chloride to alkenes

Abstract

Immediately upon mixing ICls and 2,3-dimethyl-2-butene in CCl4 at 25 °C a new absorption band due to an alkene–ICl molecular complex appears at 295 ± 5 nm and decreases rapidly with time. The rate law under conditions of (alkene)0 [Formula: see text] (ICl)0 for the electrophilic addition of ICl to 2,3-dimethyl-2-butene, E- and Z-2-butene, and E- and Z-1-phenylpropene is −d(ICl)/dt = kexpt(alkene)(ICl)3/{1 + kAD(alkene)}3 where KAD is the equilibrium constant for the formation of a 1:1 alkene–ICl molecular complex. The addition of ICl to the Z and E isomers of 2-butene and 1-phenylpropene occurs by anti-stereospecific addition. The negative enthalpy of activation for the addition of ICl to 2,3-dimethyl-2-butene is evidence that one or more complexes are involved on the reaction coordinate prior to the rate-determining step. On the basis of analysis of the enthalpy changes during the reaction, it is proposed that both a 1:1 and a 1:2 alkene–ICl molecular complex is involved in the mechanism prior to the rate-determining step.