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Synthesis and Characterization of a Copper Complex Supported by a Z‑type SbV Ligand: XPS and DFT Study of Electronic
Christopher K Webber1, Macarena G Alférez1, Farzad Bastani2
1Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.
Abstract:
We describe the synthesis and characterization of a Cu-(I) complex, {Q3Sb-(o-chlor)}-Cu-(OTf) (Q = 8-quinolinyl; OTf = trifluoromethanesulfonate; o-chlor = o-choranil), supported by the Sb-(V) ligand Q3Sb-(o-chlor). The complex {Q3Sb-(o-chlor)}-Cu-(OTf) was experimentally characterized via 1H, 13C-{1H}, and 19F-{1H} NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) as well as examined computationally with density functional theory (DFT) calculations. Variable temperature 1H NMR spectroscopy (20 to -110 °C) indicates temperature-dependent fluxional processes for {Q3Sb-(o-chlor)}-Cu-(OTf) and uncoordinated Q3Sb-(o-chlor). The electron density of Cu for {Q3Sb-(o-chlor)}-Cu-(OTf) was probed by comparing CuII/CuI redox potential and Cu 2p electron binding energies, using XPS, with a related non-Sb-containing complex, (TMQA)-Cu-(OTf) (TMQA = tris-(quinolin-2-ylmethyl)-amine). The E 1/2 of the CuII/CuI redox of {Q3Sb-(o-chlor)}-Cu-(OTf) is shifted 670 mV more positive than that of (TMQA)-Cu-(OTf). XPS spectra of {Q3Sb-(o-chlor)}-Cu-(OTf) and (TMQA)-Cu-(OTf) indicate a 0.8 eV higher Cu 2p binding energy for {Q3Sb-(o-chlor)}-Cu-(OTf). Computational studies of the molecular orbitals and localized natural bonding orbitals (NBOs) are consistent with a weak Cu-(I) → Sb-(V) interaction for {Q3Sb-(o-chlor)}-Cu-(OTf), for which Sb-(V) acts as a Z-type ligand.
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