Nitrogen fixation and reduction at boron

Currently, the only compounds known to support fixation and functionalization of dinitrogen (N2) under nonmatrix conditions are based on metals. Here we present the observation of N2 binding and reduction by a nonmetal, specifically a dicoordinate borylene. Depending on the reaction conditions under which potassium graphite is introduced as a reductant, N2 binding to two borylene units results in either neutral (B2N2) or dianionic (B2N22-) products that can be interconverted by respective exposure to further reductant or to air. The 15N isotopologues of the neutral and dianionic molecules were prepared with 15N-labeled dinitrogen, allowing observation of the nitrogen nuclei by 15N nuclear magnetic resonance spectroscopy. Protonation of the dianionic compound with distilled water furnishes a diradical product with a central hydrazido B2N2H2 unit. All three products were characterized spectroscopically and crystallographically.