Mateos-Calbet Ana, Bruzzese Paolo Cleto, Mermigki Markella Aliki, Schnegg Alexander, Pantazis Dimitrios A, Cornella Josep
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany.
Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, Mülheim an der Ruhr 45470, Germany.
J Am Chem Soc. 2025 Jun 11;147(23):19438-19443. doi: 10.1021/jacs.5c03351. Epub 2025 May 29.
To improve our understanding of Ni-catalyzed alcohol formation with NO, a catalytically relevant Ni(I)-alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with NO at ambient temperature within 1 min, producing alcohol and N. This contrasts sharply with slower reactions of (bpy)NiEt (12 h) and catalytic systems (22 h). Theoretical studies suggest a stepwise organometallic Baeyer-Villiger mechanism via a Ni(II)-oxyl intermediate. The high reactivity of Ni(I)-alkyl challenges the notion of NO's inertness, highlighting its potential as a versatile oxidant in synthesis.
为了增进我们对镍催化一氧化氮生成醇的理解，合成并表征了一种具有催化活性的镍（I）-烷基配合物（采用电子顺磁共振和核磁共振方法）。该配合物通过歧化反应和金属转移反应制备而成，在室温下与一氧化氮在1分钟内发生反应，生成醇和氮气。这与（联吡啶）镍乙基配合物的较慢反应（12小时）和催化体系的反应（22小时）形成鲜明对比。理论研究表明，反应通过镍（II）-氧基中间体按逐步有机金属拜耳-维利格机理进行。镍（I）-烷基的高反应活性对一氧化氮惰性的观念提出了挑战，突出了其在合成中作为通用氧化剂的潜力。
