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Nitrogen Trifluoride Complexes of Group 10 Transition Metals M(NF3) (M = Pd, Pt)† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc02313c

ABSTRACT: 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 dz2 orbital and π back-donation from the metal dxz/yz 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. Laser-ablated Pd and Pt atom reactions with nitrogen trifluoride have been performed in excess neon and argon matrices. N-coordination complexes [M(NF3)] were produced and further rearranged to insertion products FNMF2 on subsequent irradiation.

SUBMITTER: Deng G

PROVIDER: S-EPMC10430601 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature

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