Bent and planar structures of μ–η2:η2-N2 dinuclear early transition metal complexes

Abstract

This work studied the bent and planar structures of M₂N₂ cores of a series of dinuclear early transition-metal complexes (M = Zr, Hf, Nb, Ta, Mo and W) containing a side-on bridging dinitrogen ligand using DFT method. The calculated results propose three key factors favoring a bent structure: (1) the availability of a single electron in the metal centers which leads to the bonding interaction between two metal atoms, (2) no remarkable steric effect around the metal centers, and (3) the cis conformation of the ligands in the dinitrogen dinuclear complexes. In addition, the bent and planar structures of M₂N₂ could be transformed into each other if the steric hindrance was slight.