Structural Characterization of the [CuOR]2+ Core
Inorganic Chemistry | Physical Chemistry
Formal Cu(III) complexes bearing an oxygen-based auxiliary ligand ([CuOR]2+, R = H or CH2CF3) were stabilized by modulating the donor character of supporting ligand LY (LY = 4-Y, N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide, Y = H or OMe) and/or the basicity of the auxiliary ligand, enabling the first characterization of these typically highly reactive cores by NMR spectroscopy and X-ray crystallography. Enhanced lifetimes in solution and slowed rates of PCET with a phenol substrate were observed. NMR spectra corroborate the S = 0 ground states of the complexes, and X-ray structures reveal shortened Cu–ligand bond distances that match well with theory.
Journal of the American Chemical Society
V. M. Krishnan, D. Y. Shopov, C. J. Bouchey, W. D. Bailey, R. Parveen, B. Vlaisavljevich, and W. B. Tolman “Structural Characterization of the [CuOR]2+ Core” J. Am. Chem. Soc. 2021, 143, 9, 3295-3299.