Understanding Terminal versus Bridging End-on N2 Coordination in Transition Metal Complexes

Abstract

Terminal and bridging end-on coordination of N₂ to transition metal complexes offer possibilities for distinct pathways in ammonia synthesis and N₂ functionalization. Here we elucidate the fundamental factors controlling the two binding modes and determining which is favored for a given metal–ligand system, using both quantitative density functional theory (DFT) and qualitative molecular orbital (MO) analyses. The Gibbs free energy for converting two terminal MN₂ complexes into a bridging MNNM complex and a free N₂ molecule (2ΔG_eq^°) is examined through systematic variations of the metal and ligands; values of ΔG_eq^° range between +9.1 and −24.0 kcal/mol per M–N₂ bond. We propose a model that accounts for these broad variations by assigning a fixed π-bond order (BO^π) to the triatomic terminal MNN moiety that is equal to that of the free N₂ molecule, and a variable BO^π to the bridging complexes based on the character (bonding or antibonding) and occupancy of the π-MOs in the tetratomic MNNM core. When the conversion from terminal to bridging coordination and free N₂ is associated with an increase in the number of π-bonds (ΔBO_eq^π > 0), the bridging mode is greatly favored; this condition is satisfied when each metal provides 1, 2, or 3 electrons to the π-MOs of the MNNM core. When each metal in the bridging complex provides 4 electrons to the MNNM π-MOs, ΔBO_eq^π = 0; the equilibrium in this case is approximately ergoneutral and the direction can be shifted by dispersion interactions.

Citation

Understanding Terminal versus Bridging End-on N2 Coordination in Transition Metal Complexes

Lynn S. Yamout, Mohamad Ataya, Faraj Hasanayn, Patrick L. Holland, Alexander J. M. Miller, and Alan S. Goldman

Journal of the American Chemical Society 2021 143 (26), 9744-9757

DOI: 10.1021/jacs.1c01146