With the aim of drawing comparisons to the highly reactive complex LCuOH (L = bis(2,6-diisopropylphenylcarboxamido)pyridine), the complexes [Bu4N][LCuSR] (R = H or Ph) were prepared, characterized by spectroscopy and X-ray crystallography, and oxidized at low temperature to generate the species assigned as LCuSR on the basis of spectroscopy and theory. Consistent with the smaller electronegativity of S versus O, redox potentials for the LCuSR–/0 couples were ∼50 mV lower than for LCuOH–/0, and the rates of the proton-coupled electron transfer reactions of LCuSR with anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine at −80 °C were significantly slower (by more than 100 times) than the same reaction of LCuOH. Density functional theory (DFT) and time-dependent DFT calculations on LCuZ (Z = OH, SH, SPh) revealed subtle differences in structural and UV–visible parameters. Further comparison to complexes with Z = F, Cl, and Br using complete active space (CAS) self-consistent field and localized orbital CAS configuration interaction calculations along with a valence-bond-like interpretation of the wave functions showed differences with previously reported results (J. Am. Chem. Soc.20201428514), and argue for a consistent electronic structure across the entire series of complexes, rather than a change in the nature of the ligand field arrangement for Z = F.
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