A molecular orbital study on the interaction of dinitrogen with transition metal atoms

Interactions of single metal atoms (Cr, Fe, Ni) with N2 were studied by an ab initio MO theory. The results for free N2 and for linear MNN complexes compare well with experimental data (including UPS and XPS experiments with N2 adsorbed on transition metal surfaces).The 5σ as well as the 4σ are orbitals of N2 are involved in the bond formation. A “π-backdonation” contribution is indicated by a small electron transfer to the ligand.