PNNL

Abstract

All three hydrogen atoms of the NH3 ligand of [Mn(depe)2(CO)(NH3)]+ are abstracted in reactions with 2,4,6-tri-tert-butylphenoxyl radical, resulting in the isolation of a rare cyclophosphazenium cation [(Et2P(CH2)2PEt2)N]+, in 76% yield. Similar reactions are observed for [Mn(dppe)2(CO)(NH3)]+. Computational studies suggest that insertion of NH into a Mn-P bond provides a strong thermodynamic driving force. Contextualization of this surprising reaction in the paucity of NH3 oxidation by molecular complexes provides insights on catalyst design and breaking strong N-H bonds.