TY - JOUR
T1 - Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants
AU - Mandal, Debasish
AU - Shaik, Sason
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/3/2
Y1 - 2016/3/2
N2 - The study of C-H bond activation reactions by nonheme FeIVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.
AB - The study of C-H bond activation reactions by nonheme FeIVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.
UR - http://www.scopus.com/inward/record.url?scp=84959420453&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b12077
DO - 10.1021/jacs.5b12077
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:84959420453
SN - 0002-7863
VL - 138
SP - 2094
EP - 2097
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 7
ER -