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<p>Basic organic motifs built from carbon and nitrogen are long-established cornerstones of synthetic chemistry. Yet, it has become increasingly challenging to design new three-atom C/N assemblies with uncharted structures and properties. While organic azides (R–N<sub>3</sub>, R = organic group) and diazomethyl anions (R–CN<sub>2</sub>)<sup>−</sup> have long served as versatile synthetic platforms, their isoelectronic isodiazomethyl anion counterparts (R–NNC)<sup>−</sup> have remained elusive in the absence of transition-metal stabilization. Here we report the isolation and structural characterization of a metal-free isodiazomethyl anion. This boryl-isodiazomethyl anion features a bent eneyne-type B=N–N≡C scaffold exhibiting pronounced charge separation and a highly nucleophilic, boron-bound nitrogen centre. This characteristic enables a rare, concerted CN<sup>−</sup>/CO exchange at the nitrogen atom to yield a boryl-isocyanate, as well as easy metathesis reactions with C=O, C=S and C=N bonds. Quantum chemical calculations further reveal that the ‘U-turn’ migration of the terminal NC fragment is pivotal in driving the observed metathesis transformations.</p><p></p>

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A crystalline isodiazomethyl anion

  • 期刊论文

  • 发表日期：

    2026年1月27日

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  • Hongyu Wang,
  • Jiancheng Li,
  • Liu Leo Liu

摘要

Basic organic motifs built from carbon and nitrogen are long-established cornerstones of synthetic chemistry. Yet, it has become increasingly challenging to design new three-atom C/N assemblies with uncharted structures and properties. While organic azides (R–N3, R = organic group) and diazomethyl anions (R–CN2)− have long served as versatile synthetic platforms, their isoelectronic isodiazomethyl anion counterparts (R–NNC)− have remained elusive in the absence of transition-metal stabilization. Here we report the isolation and structural characterization of a metal-free isodiazomethyl anion. This boryl-isodiazomethyl anion features a bent eneyne-type B=N–N≡C scaffold exhibiting pronounced charge separation and a highly nucleophilic, boron-bound nitrogen centre. This characteristic enables a rare, concerted CN−/CO exchange at the nitrogen atom to yield a boryl-isocyanate, as well as easy metathesis reactions with C=O, C=S and C=N bonds. Quantum chemical calculations further reveal that the ‘U-turn’ migration of the terminal NC fragment is pivotal in driving the observed metathesis transformations.