Electron-Transfer Oxidation of Coenzyme B12Model Compounds and Facile Cleavage of the Cobalt(IV)−Carbon Bond via Charge-Transfer Complexes with Bases. A Negative Temperature Dependence of the Rates

2005 ◽  
Vol 109 (6) ◽  
pp. 1105-1113 ◽  
Author(s):  
Kei Ohkubo ◽  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Temperature Dependence ◽  
Negative Temperature ◽  
Charge Transfer Complexes ◽  
Carbon Bond

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone

1976 ◽  
Vol 54 (14) ◽  
pp. 2261-2265 ◽  
Author(s):  
Z. M. Hashish ◽  
I. M. Hoodless
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Reaction Rate ◽  
Second Order ◽  
Charge Transfer Complexes ◽  
Ion Transfer ◽  
Hydride Ion ◽  
Rate Determining Step ◽  
Hydride Ion Transfer

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone in phenetole solution has been investigated. The present work does not fully confirm earlier studies which report that the reaction follows second-order kinetics and that the hydride ion transfer is rate determining. In the investigations described in this paper second-order kinetics are only observed in the later stages of the reaction and a 1:1 stoichiometry of the reactants in the process is not obtained. Substitution of tritium in the 1,4-positions of the hydrocarbon appears to not significantly affect the reaction rate. The present results indicate that charge-transfer complexes are formed in the reaction and it is suggested that electron transfer within these complexes could be the rate-determining step in the dehydrogenation.

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