Theoretical study of resorufin reduction mechanism by NaBH4.

In the current work, the whole reduction mechanism of resorufin by sodium borohydride (NaBH4) has been investigated completely using quantum chemical theory for the first time. The possible pathways for each step were considered as much as possible. The calculated results reveal that the reduction mechanism for resorufin undergoes a nucleophilic addition with BH4(-), a synchronous proton abstraction from a carbon (C) atom, a protonation in a nitrogen (N) atom, and then a final hydrolysis process to obtain final reduced product dihydroresorufin. Interestingly, it was found that the protonation of N atom could induce a reduced product molecule with a Λ-type structure rather than a planar one, and the large alteration in geometry will induce different optical properties, such as fluorescent or nonfluorescent. More importantly, countercation Na(+) and solvation effect of H2O play important roles in reducing the activation energy in elementary steps, and their stabilization effect has been confirmed by NBO analysis. The detailed theoretical investigation for the reduction reaction of resorufin by NaBH4 will support some guidance for the similar reduction reaction for organic compounds like aldehydes and ketones.