Kinetic isotope effect is a sensitive probe of spin state reactivity in C-H hydroxylation of N,N-dimethylaniline by cytochrome P450.
This paper presents DFT calculations of C-H hydroxylation of N,N-dimethylaniline by Compound I (Cpd I) of cytochrome P450. The reaction involves two processes nascent from the two spin states of Cpd I, the low-spin (LS) and high-spin (HS) states. The calculations demonstrate that the kinetic isotope effects (KIEs) of the two processes are very different, and only KIELS fits the experimental datum. As such, KIE can be a sensitive probe of spin state reactivity.
Li
Chunsen
C
State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, and Department of Chemistry, Xiamen University, PR China.
Wu
Wei
W
Kumar
Devesh
D
Shaik
Sason
S
D000814:Aniline Compounds / Q000737:chemistry* / Q000378:metabolism; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry* / Q000378:metabolism; D006900:Hydroxylation; D007700:Kinetics; D008958:Models, Molecular; D013816:Thermodynamics
D000814:Aniline Compounds; C015157:N,N-dimethylaniline; D003577:Cytochrome P-450 Enzyme System