title: Enthalpy versus entropy in chlorocarbene/alkene addition reactions.
abstract: We report the first measured activation parameters for the additions of CCl2 and CClF to simple alkenes and demonstrate the existence of enthalpic barriers for CCl2 additions to cyclohexene and 1-hexene. With these two alkenes, additions of PhCCl are "dominated" by entropic contributions to deltaG++ and additions of CCl2 display comparable contributions of deltaH++ and deltaS++, while CClF additions feature dominant enthalpic contributions to deltaG++. Entropic factors, however, control the additions of all three carbenes to the highly reactive alkene, tetramethylethylene. Parallel computational studies are also reported.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA. moss@rutchem.rutgers.edu
authors.forename: Robert A
authors.initials: RA
authors.lastname: Moss
authors.forename: Lei
authors.initials: L
authors.lastname: Wang
authors.forename: Min
authors.initials: M
authors.lastname: Zhang
authors.forename: Christopher
authors.initials: C
authors.lastname: Skalit
authors.forename: Karsten
authors.initials: K
authors.lastname: Krogh-Jespersen