biostudies-literatureWu WDivision of ChemistryNational Institute of General Medical SciencesNIGMS NIH HHSNational Science Foundation5217-5223https://www.ebi.ac.uk/biostudies/studies/S-EPMC8094167biostudies-literatureUnknown60(7)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-dependenInorganic chemistrySulfur-Containing Analogues of the Reactive [CuOH]²⁺ Core.PMC8094167R37 GM047365OAC-1626516R01 GM0473651827756GM47365Tolman WBDe Hont JTWu WVlaisavljevich BParveen RfalseSulfur-Containing Analogues of the Reactive [CuOH]²⁺ Core.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-dependen2021-01-01T00:00:00Z2021 Apr2025-04-05T09:05:26.796Z2025-02-18T23:32:17.697ZS-EPMC80941673373375510.1021/acs.inorgchem.1c00216