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<p>The isolation and characterization of metal-stabilized, low-valent nitrogen species remain central challenges in advancing nitrogen-atom transfer chemistry. Although gold has emerged as a powerful catalyst in C–N bond formation, proposed mechanisms have consistently bypassed gold nitrenes as key intermediates—leaving their chemistry largely uncharted. Here we report the characterization of a bona fide aura-nitrene, formed via photochemical N<sub>2</sub> extrusion from a gold(III) azide complex. In crystallo and solid-state analyses reveal a diverse reactivity landscape, including a nitrene-to-nitro transformation via O<sub>2</sub> activation, intra- and intermolecular C–H bond activation, CO fixation and alkyne addition/sigmatropic rearrangement. Computational investigations confirm a triplet ground state, with the nitrene best described as a nitrogen-centred diradical <i>σ</i>-bonded to a formal gold(III) centre. These findings highlight the dual electrophilic and diradical character of gold(III) metallonitrenes and establish a conceptual framework for gold-mediated nitrogen-atom transfer beyond conventional mechanistic paradigms.</p><p></p>

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A photogenerated triplet aura-nitrene for gold-mediated nitrene transfer

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年7月21日

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  • Jaime Martín,
  • Marc Fernández-Sabaté,
  • Bernhard Spingler,
  • John H. Beale,
  • Dominik Munz,
  • Cristina Nevado

摘要

The isolation and characterization of metal-stabilized, low-valent nitrogen species remain central challenges in advancing nitrogen-atom transfer chemistry. Although gold has emerged as a powerful catalyst in C–N bond formation, proposed mechanisms have consistently bypassed gold nitrenes as key intermediates—leaving their chemistry largely uncharted. Here we report the characterization of a bona fide aura-nitrene, formed via photochemical N2 extrusion from a gold(III) azide complex. In crystallo and solid-state analyses reveal a diverse reactivity landscape, including a nitrene-to-nitro transformation via O2 activation, intra- and intermolecular C–H bond activation, CO fixation and alkyne addition/sigmatropic rearrangement. Computational investigations confirm a triplet ground state, with the nitrene best described as a nitrogen-centred diradical σ-bonded to a formal gold(III) centre. These findings highlight the dual electrophilic and diradical character of gold(III) metallonitrenes and establish a conceptual framework for gold-mediated nitrogen-atom transfer beyond conventional mechanistic paradigms.