Acid-catalysed reduction of p-benzoquinone derivatives by an NADH analogue, 9,10-dihydro-10-methylacridine. The energetic comparison of one-electron vs. two-electron pathways

Abstract
The energetic comparison of one-electron vs. two-electron pathways has been made for the acid-catalysed reduction of a series of p-benzoquinone derivatives (Q) by an NADH analogue, 9,10-dihydro-l0-methylacridine (AcrH2), in aqueous solutions (H2O–EtOH; 5:1 v/v) at 298 K. The pH dependences of the second-order rate constants (log kobs) as well as the primary kinetic isotope effects (kH/kD) for the acid-catalysed reduction of Q by AcrH2 have been correlated well with the pH dependences of the one-electron reduction potentials of p-benzoquinone derivatives. On the other hand, no direct correlation of log kobs or kH/kD with the corresponding two-electron reduction potentials has been observed. Mechanisms of the acid-catalysed hydride transfer reactions from AcrH2 to Q have been discussed based on the energetic comparison of one-electron vs. two-electron pathways.

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