Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe

The geometric constraints imposed by a tetradentate P4N2 ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe0(N2)­(P4N2) complex catalyzes the conversion of N2 to N­(SiR3)3 (R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N2 silylation catalyst to date (up to 65 equiv N­(SiMe3)3 per Fe center). Elevated N2 pressures (>1 atm) have a dramatic effect on catalysis, increasing N2 solubility and the thermodynamic N2 binding affinity at Fe0(N2)­(P4N2). A combination of high-pressure electrochemistry and variable-temperature UV–vis spectroscopy were used to obtain thermodynamic measurements of N2 binding. In addition, X-ray crystallography, 57Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe0, FeI, and FeII complexes reveals that the free energy of N2 binding across three oxidation states spans more than 37 kcal mol–1.