Thermodynamics-inspired identification of privileged organocatalysts for hydrogen evolution reactions.

Abstract

The 7π-aromaticity observed in N-heterocyclic phosphinyl radicals (NHP˙) can offset the energy penalty associated with the disruption of 6π-aromaticity in NHP cations. This property endows NHP hydrides with facile regeneration, rendering NHP privileged organocatalysts for electrochemical hydrogen evolution reactions.