6533b86efe1ef96bd12cc090

RESEARCH PRODUCT

Extending Limits of Chlorine Kinetic Isotope Effects

Katarzyna ŚWiderekPiotr Paneth

subject

ChemistryOrganic ChemistryRadiochemistryAnalytical chemistrySemiclassical physicschemistry.chemical_element010501 environmental sciences010402 general chemistryKinetic energy01 natural sciences0104 chemical sciencesAtomKinetic isotope effectpolycyclic compoundsChlorinePhysics::Atomic PhysicsPhysics::Chemical PhysicsNuclear ExperimentAstrophysics::Galaxy Astrophysics0105 earth and related environmental sciences

description

Chlorine kinetic isotope effects exceeding semiclassical limits were observed in enzyme-catalyzed reactions, but their source has not been yet identified. Herein we show that unusually large chlorine kinetic isotope effects are associated with reactions in which chlorine is the central atom that is being passed between two heavy atoms. The origin of these large values is the ratio of imaginary frequencies for light-to-heavy species (the so-called temperature-independent factor).

https://doi.org/10.1021/jo300682f