Nitrogen Trifluoride Complexes of Group 10 Transition Metals M(NF₃) (M = Pd, Pt)

The group 10 transition metal atoms Pd and Pt react with nitrogen trifluoride (NF₃) forming N-coordination M(NF₃) complexes in solid neon and argon matrices. The M(NF₃) complexes isomerize to more stable fluoronitrenoid FNMF₂ isomers via fluorine migration upon blue LED (λ = 470 nm) light irradiation. These products are characterized on the basis of infrared absorption spectroscopy with isotopic substitutions and theoretical frequency calculations. The analysis of the electronic structure of nitrogen trifluoride complexes indicates that the bonding between metal and nitrogen trifluoride can be described as σ donation from the HOMO of nitrogen trifluoride to the empty metal d orbital and π back-donation from the metal d orbitals to the LUMO of nitrogen trifluoride, the latter of which stabilized the metal ligand bond and destabilized the ligand N-F bond. In FNMF₂, the FN ligand doubly bonded to the metal and bear imido character.