Calculations predict a large inverse H/D kinetic isotope effect on the rate of tunneling in the ring opening of cyclopropylcarbinyl radical.
B3LYP/6-31G* calculations have been performed, to compute the kinetic isotope effects (KIEs) on the rate of ring opening of cyclopropylcarbinyl radical (1) to 3-buten-1-yl radical (2) at 20 K by tunneling. The most striking result of our small curvature tunneling calculations is the prediction of a 2.7-fold increase in the rate of reaction by substitution of D(2) for H(2) at C(1). The origin of this very surprising, inverse KIE on the rate of tunneling is discussed.
Zhang
Xue
X
Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle #305070, Denton, Texas 76203-5017, USA.
Datta
Ayan
A
Hrovat
David A
DA
Borden
Weston Thatcher
WT