Premium
Four‐Coordinate Copper Halonitrosyl {CuNO} 10 Complexes
Author(s) -
Bower Jamey K.,
Sokolov Alexander Yu.,
Zhang Shiyu
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904732
Subject(s) - copper , chemistry , bromide , nucleophile , photochemistry , polymer chemistry , inorganic chemistry , organic chemistry , catalysis
While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl 3 CuNO] − , 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, [Br 3 CuNO] − 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 Cu II –NO . ground state. Both [Cl 3 CuNO] − and [Br 3 CuNO] − release and recapture NO . reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.