Four‐Coordinate Copper Halonitrosyl {CuNO}10 Complexes

• Published in: Angewandte Chemie Vol. 131; no. 30; pp. 10331 - 10335
• Main Authors: Bower, Jamey K., Sokolov, Alexander Yu, Zhang, Shiyu
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 22-07-2019
• Subjects: Alcohols; Amines; Chemistry; Chlorides; Coordination compounds; Copper; Copper compounds; Dichlorides; Elektronische Struktur; Kupfer; Nitric oxide; Nitritreduktion; Nitrosyl-Liganden; Nucleophiles; Reduktive Nitrosylierung; Thiols; X-ray diffraction
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201904732

While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3CuNO]−, with a {CuNO}10 electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3CuNO]− was synthesized analogously, and both copper halonitrosyl complexes were characterized by X‐ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a CuII–NO. ground state. Both [Cl3CuNO]− and [Br3CuNO]− release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.
Jagd auf Dr. NO: Seit mehr als 100 Jahren weiß man, dass Kupferhalogenide Stickstoffmonoxid absorbieren, die Strukturen der Produkte wurden jedoch nie aufgeklärt. Seltene {CuNO}10‐Spezies, die reversibel Stickstoffmonoxid binden – TBA[Cl3CuNO] und TBA[Br3CuNO] –, wurden nun hergestellt und strukturell charakterisiert.