A Contrasting Effect of Acid in Electron Transfer, Oxygen Atom Transfer, and Hydrogen Atom Transfer Reactions of a...

There have been many examples of the accelerating effects of acids in electron transfer (ET), oxygen atom transfer (OAT), and hydrogen atom transfer (HAT) reactions. Herein, we report a contrasting effect of acids in the ET, OAT, and HAT reactions of a nickel(III) complex, [Ni^III(PaPy₃*)]²⁺ (1) in acetone/CH₃CN (v/v 19:1). 1 was synthesized by reacting [Ni^II(PaPy₃*)]⁺ (2) with magic blue or iodosylbenzene in the absence or presence of triflic acid (HOTf), respectively. Sulfoxidation of thioanisole by 1 and H₂O occurred in the presence of HOTf, and the reaction rate increased proportionally with increasing concentration of HOTf ([HOTf]). The rate of ET from diacetylferrocene to 1 also increased linearly with increasing [HOTf]. In contrast, HAT from 9,10-dihydroanthracene (DHA) to 1 slowed down with increasing [HOTf], exhibiting an inversely proportional relation to [HOTf]. The accelerating effect of HOTf in the ET and OAT reactions was ascribed to the binding of H⁺ to the PaPy₃* ligand of 2; the one-electron reduction potential (E_red) of 1 was positively shifted with increasing [HOTf]. Such a positive shift in the E_red value resulted in accelerating the ET and OAT reactions that proceeded via the rate-determining ET step. On the other hand, the decelerating effect of HOTf on HAT from DHA to 1 resulted from the inhibition of proton transfer from DHA^•+ to 2 due to the binding of H⁺ to the PaPy₃* ligand of 2. The ET reactions of 1 in the absence and presence of HOTf were well analyzed in light of the Marcus theory of ET in comparison with the HAT reactions.