Intramolecular kinetic isotope effect in hydride transfer from dihydroacridine to a quinolinium ion. Rejection of a proposed two-step mechanism with a kinetically significant intermediate

2008 ◽  
Vol 6 (18) ◽  
pp. 3349 ◽  
Author(s):  
Charles L. Perrin ◽  
Chen Zhao
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Hydride Transfer ◽  
Kinetic Isotope ◽  
Ion Rejection ◽  
Step Mechanism

Hydride transfer from NADH analogues to a nonheme manganese(iv)–oxo complex via rate-determining electron transfer

2014 ◽  
Vol 50 (85) ◽  
pp. 12944-12946 ◽  
Author(s):  
Heejung Yoon ◽  
Yong-Min Lee ◽  
Wonwoo Nam ◽  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Hydride Transfer ◽  
Charge Transfer Complexes ◽  
Kinetic Isotope ◽  
Transfer Step

Hydride transfer from NADH analogues to a nonheme Mn(iv)–oxo complex, [(Bn-TPEN)MnIV(O)]2+, proceeds via a rate-determining electron transfer step with no deuterium kinetic isotope effect (KIE = 1.0 ± 0.1) and via charge-transfer complexes formed in the reactions of Mn(iv)–oxo and NADH analogues.

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