title: Light- and heavy-atom tunneling in rearrangement reactions of cyclopropylcarbenes.
abstract: We investigated both light- and heavy-atom tunneling in the rearrangements of a series of cyclopropylcarbenes using canonical variational transition state theory with multidimensional tunneling corrections (CVT/MT) and the Wentzel-Kramers-Brillouin (WKB) formalism. Halogeno- and hydroxy-substituted cyclopropylcarbenes were found not to undergo carbon tunneling owing to wide reaction barriers. However, while carbon tunneling plays a major role in the ring expansion of parent cyclopropylcarbene yielding cyclobutene, cyclopropylmethylcarbene is prone to undergo hydrogen tunneling to give cyclopropylmethylene.
authors.affiliation: Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany.
authors.forename: Dennis
authors.initials: D
authors.lastname: Gerbig
authors.forename: David
authors.initials: D
authors.lastname: Ley
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner