Heteroscorpionate ligands of the bis(pyrazolyl)methane family have been applied in the stabilisation of terminal copper tosyl nitrenes. These species are highly active intermediates in the copper‐catalysed direct C−H amination and nitrene transfer. Novel perfluoroalkyl‐pyrazolyl‐ and pyridinyl‐containing ligands were synthesized to coordinate to a reactive copper nitrene centre. Four distinct copper tosyl nitrenes were prepared at low temperatures by the reaction with SO₂tBuPhINTs and copper(I) acetonitrile complexes. Their stoichiometric reactivity has been elucidated regarding the imination of phosphines and the aziridination of styrenes. The formation and thermal decay of the copper nitrenes were investigated by UV/Vis spectroscopy of the highly coloured species. Additionally, the compounds were studied by cryo‐UHR‐ESI mass spectrometry and DFT calculations. In addition, a mild catalytic procedure has been developed where the copper nitrene precursors enable the C−H amination of cyclohexane and toluene and the aziridination of styrenes.

中文翻译：

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设计用于反应：末端铜镍及其在催化CH胺中的应用

双（吡唑基）甲烷家族的异蝎子酸酯配体已被用于稳定铜甲苯磺腈的末端。这些物质是铜催化的直接CHH胺化和腈转移中的高活性中间体。合成了新的含全氟烷基吡唑基和吡啶基的配体，以与反应性的铜氮烯中心配位。通过与SO ₂ t反应，在低温下制备了四种不同的甲苯磺酰基铜腈BuPhINTs和铜（I）乙腈络合物。关于膦的亚胺化和苯乙烯的叠氮化，已经阐明了它们的化学计量反应性。通过高度着色物质的UV / Vis光谱研究了铜氮烯的形成和热衰变。此外，还通过冷冻UHR-ESI质谱和DFT计算研究了这些化合物。此外，已经开发了一种温和的催化程序，其中铜亚硝基前体能够实现环己烷和甲苯的CH氨化以及苯乙烯的叠氮化。