Ontology highlight
ABSTRACT:
SUBMITTER: Wilson PB
PROVIDER: S-EPMC4770435 | biostudies-literature | 2016 Feb
REPOSITORIES: biostudies-literature
Wilson Philippe B PB Williams Ian H IH
Angewandte Chemie (International ed. in English) 20160128 9
DFT calculations for methyl cation complexed within a constrained cage of water molecules permit the controlled manipulation of the "axial" donor/acceptor distance and the "equatorial" distance to hydrogen-bond acceptors. The kinetic isotope effect k(CH3)/k(CT3) for methyl transfer within a cage with a short axial distance becomes less inverse for shorter equatorial C⋅⋅⋅O distances: a decrease of 0.5 Å results in a 3 % increase at 298 K. Kinetic isotope effects in AdoMet-dependent methyltransfer ...[more]