Title

Structural Characterization of the [CuOR]2+ Core

Document Type

Article

Publication Date

2-23-2021

Disciplines

Inorganic Chemistry | Physical Chemistry

Abstract

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.

Publication Title

Journal of the American Chemical Society

Volume

143

Issue

9

First Page

3295

Last Page

3299

DOI

10.1021/jacs.0c13470

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