(Electro)chemical N₂ Splitting by a Molybdenum Complex with an Anionic PNP Pincer-Type Ligand

Molybdenum(III) complexes bearing pincer-type ligands are well-known catalysts for N2-to-NH3 reduction. We investigated herein the impact of an anionic PNP pincer-type ligand in a Mo(III) complex on the (electro)chemical N2 splitting ([LMoCl3]−, 1–, LH = 2,6-bis((di-tert-butylphosphaneyl)methyl)-pyridin-4-one). The increased electron-donating properties of the anionic ligand should lead to a stronger degree of N2 activation. The catalyst is indeed active in N2-to-NH3 conversion utilizing the proton-coupled electron transfer reagent SmI2/ethylene glycol. The corresponding Mo(V) nitrido complex 2H exhibits similar catalytic activity as 1H and thus could represent a viable intermediate. The Mo(IV) nitrido complex 3– is also accessible by electrochemical reduction of 1– under a N2 atmosphere. IR- and UV/vis-SEC measurements suggest that N2 splitting occurs via formation of an "overreduced" but more stable [(L(N2)2Mo0)2μ-N2]2– dimer. In line with this, the yield in the nitrido complex increases with lower applied potentials.