The highly reactive LCuOH complex (L = bis(2,6-diisopropylphenylcarboxamido)pyridine) and its sulfur analog have been studied with density functional theory (DFT) and multireference complete active space (CASSCF) methods to provide insights into its electronic structure and UV-Vis spectra. Here we present how DFT and time-dependent DFT calculations on LCuZ (Z = OH, SH, SPh, F, Cl, and Br) can reveal subtle differences in structural and UV–visible parameters. Furthermore, CASSCF calculations are compared with so-called localized orbital CAS configuration interaction calculations that can be used to obtain a valence-bond-like interpretation of the wave functions show how the latter approach can be used to assess the percent contribution of Cu(II) and Cu(III) electronic configurations to the total wavefunction. A consistent electronic structure is observed across the entire series of complexes.

Electronic structure of the reactive [CuOH]<sup>2+</sup> core and its analogs

ACS Spring 2022

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Electronic structure of the reactive [CuOH]2+ core and its analogs

Electronic structure of the reactive [CuOH]²⁺ core and its analogs