Sulfur-Containing Analogues of the Reactive [CuOH]²⁺ Core.

ABSTRACT: 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-dependen

SUBMITTER: Wu W 

PROVIDER: S-EPMC8094167 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature