Chromium Complexes with Benzanellated N‐heterocyclic Phosphenium Ligands – Synthesis, Reactivity and Application in Catalytic CO2 Reduction

Abstract A chromium complex carrying two benzanellated N‐heterocyclic phosphenium (bzNHP) ligands was prepared by a salt metathesis approach. Spectroscopic studies suggest that the anellation enhances the π‐acceptor ability of the NHP‐units, which is confirmed by the facile electrochemical reduction of the complex to a spectroscopically characterized radical anion. Co‐photolysis with H 2 allowed extensive conversion into a σ‐H 2 ‐complex, which shows a diverse reactivity towards donors and isomerizes under H−H bond fission and shift of a hydride to a P‐ligand. The product carrying phosphenium, phosphine and hydride ligands was also synthesized independently and reacts reversibly with CO and MeCN to yield bis‐phosphine complexes under concomitant Cr‐to‐P‐shift of a hydride. In contrast, CO 2 was not only bound but reduced to give an isolable formato complex, which reacted with ammonia borane under partial recovery of the metal hydride and production of formate. Further elaboration of the reactions of the chromium complexes with CO 2 and NH 3 BH 3 allowed to demonstrate the feasibility of a Cr‐catalyzed transfer hydrogenation of CO 2 to methanol. The various complexes described were characterized spectroscopically and in several cases by XRD studies. Further insights in reactivity patterns were provided through (spectro)electrochemical studies and DFT calculations.