Theoretical Investigation of Large Kinetic Isotope Effects for Proton-Coupled Electron Transfer in Ruthenium Polypyridyl Complexes

2002 ◽  
Vol 124 (17) ◽  
pp. 4848-4856 ◽  
Author(s):  
Nedialka Iordanova ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Theoretical Investigation ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Ruthenium Polypyridyl ◽  
Polypyridyl Complexes ◽  
Proton Coupled Electron Transfer ◽  
Kinetic Isotope ◽  
Ruthenium Polypyridyl Complexes

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

scholarly journals Colossal kinetic isotope effects in proton-coupled electron transfer

2004 ◽  
Vol 101 (36) ◽  
pp. 13138-13141 ◽  
Author(s):  
M. H. V. Huynh ◽  
T. J. Meyer
Keyword(s):  
Electron Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Proton Coupled Electron Transfer ◽  
Kinetic Isotope

scholarly journals Analysis of Kinetic Isotope Effects for Proton-Coupled Electron Transfer Reactions†

2009 ◽  
Vol 113 (10) ◽  
pp. 2117-2126 ◽  
Author(s):  
Sarah J. Edwards ◽  
Alexander V. Soudackov ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
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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