TY - JOUR
AU - Pak, Youngshang
AB -  Hybrid quantum mechanical/molecular mechanical electronic structure calculations reveal the transition state for C–H bond cleavage in [(LCu)2 (μ-O)2]2+ (L=1,4,7-tribenzyl-1,4,7-triazacyclononane) to be consistent with a hydrogen-atom-transfer mechanism from carbon to oxygen. At the MPW1K/double-zeta effective core potential(+)|univeral force field level, 0 K activation enthalpies for the parent, p-CF3, and p-OH substituted benzyl systems are predicted to be 8.8, 9.5, and 7.8 kcal/mol. Using a one-dimensional Eckart potential to estimate quantum effects on the reaction coordinate, reaction in the unsubstituted system is predicted to proceed with a primary kinetic isotope effect of 22 at 233 K. Structural parameters associated with the hydrogen-atom transfer are consistent with the Hammond postulate.
TI - Transition state for intramolecular C–H bond cleavage in [(LCu)2(μ-O)2]2+ (L = 1,4,7-tribenzyl-1,4,7-triazacyclononane)
JO - Theoretical Chemistry Accounts
DO - 10.1007/s002140000238
DA - 2001-05-07
UR - https://www.deepdyve.com/lp/springer-journals/transition-state-for-intramolecular-c-h-bond-cleavage-in-lcu-2-o-2-2-l-mFGb50Hb2H
SP - 477
EP - 480
VL - 105
IS - 6
DP - DeepDyve
ER -