Selective Iron-Catalyzed <i>N</i>‑Formylation of Amines using Dihydrogen and Carbon Dioxide

A family of iron­(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the <i>N-</i>formylation of amines via CO₂ hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the <i>N-</i>formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that <i>N-</i>formylation occurs via an initial, reversible reduction of CO₂ to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized