Kinetic Isotope Effects for Electron-Transfer Pathways in the Oxidative C−H Activation of Hydrocarbons

1998 ◽  
Vol 120 (12) ◽  
pp. 2826-2830 ◽  
Author(s):  
T. M. Bockman ◽  
S. M. Hubig ◽  
J. K. Kochi
Keyword(s):  
Electron Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Electron Transfer Pathways ◽  
Activation Of Hydrocarbons

Kinetic isotope effects in proton coupled electron transfer

2012 ◽  
Vol 668 ◽  
pp. 66-72 ◽  
Author(s):  
Wenbin Zhang ◽  
Ian J. Burgess
Keyword(s):  
Electron Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Proton Coupled Electron Transfer ◽  
Kinetic Isotope

Kinetics and mechanism of oxidation of N,N′-dimethyl-9,9′-biacridanyl by some π acceptors and a one-electron oxidant

1985 ◽  
Vol 63 (2) ◽  
pp. 445-451 ◽  
Author(s):  
Allan K. Colter ◽  
Charles C. Lai ◽  
A. Gregg Parsons ◽  
N. Bruce Ramsey ◽  
Gunzi Saito
Keyword(s):  
Electron Transfer ◽  
Reduction Potential ◽  
Isotope Effects ◽  
Substituent Effects ◽  
Kinetic Isotope Effects ◽  
Spin Trapping ◽  
Single Electron Transfer ◽  
Kinetic Isotope ◽  
The One ◽  
Rule Out

Oxidation of N,N′-dimethyl-9,9′-biacridanyl (DD) has been investigated as a model for single electron transfer (SET)-initiated oxidation of NADH coenzyme models such as N-methylacridan (DH). Oxidants investigated cover a 1010-fold range of reactivity in acetonitrile and include the π acceptors 1,4-benzoquinone (BQ), 2,6-dichloro-1,4-benzoquinone (DCIBQ), p-chloranil (CA), 2,3-dicyanobenzoquinone (DCBQ), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 2,3-dicyano-5-nitro-1,4-naphthoquinone (DCNNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DCMTNF), 9-dicyanomethylene-2,4,5,7-tetranitrofluorene (DCMTENF), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and tetracyanoethylene (TCNE), and the one-electron oxidant tris(2,2′-bipyridyl)cobalt(III), [Formula: see text] The oxidation product is, in every case, N-methylacridinium ion (D+). A mechanism involving a rate-determining electron transfer with simultaneous fragmentation to D+ and N-methyl-9-acridanyl radical (D•) is proposed. This mechanism is supported by the observed dependence of the rate on oxidant reduction potential, by spin-trapping experiments, by kinetic isotope effects in oxidation of 9,9′-dideuterio-DD, and by substituent effects in oxidation of 2,2′- and 3,3′-dimethoxy-DD. The rate of oxidation of DD relative to that of DH is 3.4 × 102 with [Formula: see text] and with the π acceptors varies from ea. 0.3 (BQ) to 8.1 × 104 (DCMTENF). The results rule out a SET-initiated mechanism for oxidation of DH by all of the oxidants studied except TCNQ and DCMTENF.

scholarly journals Kinetic Isotope Effects and Electron Transfer in the Reduction of Xanthine Oxidoreductase with 4-Hydroxypyrimidine

1997 ◽  
Vol 272 (36) ◽  
pp. 22514-22525 ◽  
Author(s):  
Christopher M. Harris ◽  
Vincent Massey
Keyword(s):  
Electron Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Xanthine Oxidoreductase ◽  
Kinetic Isotope
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