Currently, the only compounds known to support fixation and functionalization of dinitrogen (N) under nonmatrix conditions are based on metals. Here we present the observation of N binding and reduction by a nonmetal, specifically a dicoordinate borylene. Depending on the reaction conditions under which potassium graphite is introduced as a reductant, N binding to two borylene units results in either neutral (BN) or dianionic ([BN]) products that can be interconverted by respective exposure to further reductant or to air. The N isotopologues of the neutral and dianionic molecules were prepared withN-labeled dinitrogen, allowing observation of the nitrogen nuclei by N nuclear magnetic resonance spectroscopy. Protonation of the dianionic compound with distilled water furnishes a diradical product with a central hydrazido BNH unit. All three products were characterized spectroscopically and crystallographically.
The coupling of two or more molecules of dinitrogen (N2) occurs naturally under the radiative conditions present in the ionosphere and may be achieved synthetically under ultrahigh pressure or plasma conditions. However, the comparatively low N–N single-bond enthalpy generally renders the catenation of the strongly triple-bonded N2diatomic unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, we report the surprising organoboron-mediated catenation of two N2molecules under near-ambient conditions to form a complex in which a [N4]2–chain bridges two boron centers. The reaction entails reductive coupling of two hypovalent-boron-bound N2units in a single step. Both this complex and a derivative protonated at both ends of the chain were characterized crystallographically.
Recent years have witnessed rapid advances in the field of BN/CC isosterism, particularly in the case of azaborinines. Examples of each isomer have now been synthesized and characterized. This review provides a survey of the latest
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.