CO‐Induced Dinitrogen Fixation and Cleavage Mediated by Boron

The boron atoms react with carbon monoxide and dinitrogen forming the end‐on bonded NNBCO complex in solid neon or in nitrogen matrices. The NNBCO complex rearranges to the (η (2)‐N(2))BCO isomer with a more activated side‐on bonded dinitrogen ligand upon visible light excitation. (η (2)‐N(2))BCO and its weakly CO‐coordinated complexes further isomerize to the NBNCO and B(NCO)(2) molecules with N−N bond being completely cleaved under UV light irradiation. The geometries, energies and vibrational spectra of the molecules are calculated with quantum chemical methods and the electronic structures are analyzed with charge‐ and energy‐partitioning methods.