Tao Wenjie, Carter Samantha, Trevino Regina, Zhang Weiyao, Shafaat Hannah S, Zhang Shiyu
Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
J Am Chem Soc. 2022 Dec 14;144(49):22633-22640. doi: 10.1021/jacs.2c09523. Epub 2022 Dec 5.
Treatment of a dicopper(I,I) complex with excess amounts of NO leads to the formation of a dicopper dinitrosyl [Cu(NO)] complex capable of (i) releasing two equivalents of NO reversibly in 90% yield and (ii) reacting with another equivalent of NO to afford NO and dicopper nitrosyl oxo species [Cu(NO)(O)]. Resonance Raman characterization of the [Cu(NO)] complex shows a N-sensitive N═O stretch at 1527.6 cm and two Cu-N stretches at 390.6 and 414.1 cm, supporting a symmetric diamond-core structure with bis-μ-NO ligands. The conversion of [Cu(NO)] to [Cu(NO)O] occurs via a rate-limiting reaction with NO and bypasses the dicopper oxo intermediate, a mechanism distinct from that of diFe-mediated NO reduction to NO.
用过量的NO处理二价铜（I，I）配合物会导致形成一种二铜二亚硝酰基[Cu(NO)]配合物，该配合物能够（i）以90%的产率可逆地释放两当量的NO，并且（ii）与另一当量的NO反应生成NO和二铜亚硝酰基氧物种[Cu(NO)(O)]。[Cu(NO)]配合物的共振拉曼表征显示在1527.6 cm处有一个对N敏感的N═O伸缩振动以及在390.6和414.1 cm处有两个Cu-N伸缩振动，这支持了具有双-μ-NO配体的对称菱形核结构。[Cu(NO)]向[Cu(NO)O]的转化通过与NO的限速反应发生，绕过了二铜氧中间体，这是一种不同于二铁介导的NO还原为NO的机制。
