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Synthesis and Characterization of a Copper Complex Supported by a Z-type Sb V Ligand: XPS and DFT Study of Electronic Structure

Year: 2026

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide We describe the synthesis and characterization of a Cu(I) complex, {Q 3 Sb( o -chlor)}Cu(OTf) (Q = 8-quinolinyl; OTf = trifluoromethanesulfonate; o -chlor = o -choranil), supported by the Sb(V) ligand Q 3 Sb( o -chlor). The complex {Q 3 Sb( o -chlor)}Cu(OTf) was experimentally characterized via 1 H, 13 C{ 1 H}, and 19 F{ 1 H} 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 1 H NMR spectroscopy (20 to −110 °C) indicates temperature-dependent fluxional processes for {Q 3 Sb( o -chlor)}Cu(OTf) and uncoordinated Q 3 Sb( o -chlor). The electron density of Cu for {Q 3 Sb( o -chlor)}Cu(OTf) was probed by comparing Cu II /Cu I 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 Cu II /Cu I redox of {Q 3 Sb( o -chlor)}Cu(OTf) is shifted 670 mV more positive than that of (TMQA)Cu(OTf). XPS spectra of {Q 3 Sb( o -chlor)}Cu(OTf) and (TMQA)Cu(OTf) indicate a 0.8 eV higher Cu 2p binding energy for {Q 3 Sb( 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 {Q 3 Sb( o -chlor)}Cu(OTf), for which Sb(V) acts as a Z-type ligand.

Source: Organometallics

DOI: 10.1021/acs.organomet.5c00420