Spectroscopic Evidence for a 3d(10) Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF3)4](1-)

J Am Chem Soc. 2016 Feb 17;138(6):1922-31. doi: 10.1021/jacs.5b10819. Epub 2016 Feb 4.

Abstract

The contested electronic structure of [Cu(CF3)4](1-) is investigated with UV/visible/near IR spectroscopy, Cu K-edge X-ray absorption spectroscopy, and 1s2p resonant inelastic X-ray scattering. These data, supported by density functional theory, multiplet theory, and multireference calculations, support a ground state electronic configuration in which the lowest unoccupied orbital is of predominantly trifluoromethyl character. The consensus 3d(10) configuration features an inverted ligand field in which all five metal-localized molecular orbitals are located at lower energy relative to the trifluoromethyl-centered σ orbitals.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Copper / chemistry*
  • Ligands
  • Spectrum Analysis / methods*

Substances

  • Ligands
  • Copper