Protonation and electrochemical reduction of rhodium- and iridium-dinitrogen complexes in organic solution.

Protonation and reduction of pincer-ligated Rh- and Ir-N complexes have been studied by NMR spectroscopy and cyclic voltammetry to assess the capability of these complexes to activate or reduce N. Protonation, which is a prerequisite to electrochemical reduction, results in a cationic metal-hydride that loses N under an atmosphere of Ar. Reduction of the metal-hydride results in fast disproportionation of an unobserved transient Ir species. These studies suggest that the regioselectivity of initial protonation is a strong determinant for the ability of a system to facilitate the reduction of N.