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Single-Crystal X-ray Structure Determination of Tris(pyrazol-1-yl)methane Triphenylphosphine Copper(I) Tetrafluoroborate, Hirshfeld Surface Analysis and DFT Calculations
oleh: Jesús Castro, Valentina Ferraro, Marco Bortoluzzi
| Format: | Article |
|---|---|
| Diterbitkan: | MDPI AG 2024-02-01 |
Deskripsi
The tetrafluoroborate salt of the cationic Cu(I) complex [Cu(CHpz<sub>3</sub>)(PPh<sub>3</sub>)]<sup>+</sup>, where CHpz<sub>3</sub> is the tridentate N-donor ligand tris(pyrazol-1-yl)methane and PPh<sub>3</sub> is triphenylphosphine, was synthesized through a displacement reaction on the acetonitrile complex [Cu(NCCH<sub>3</sub>)<sub>4</sub>][BF<sub>4</sub>]. The compound crystallizes in the monoclinic <i>P</i>2<sub>1</sub>/<i>c</i> space group. The single-crystal X-ray diffraction revealed that the copper(I) centre is tetracoordinated, with a disposition of the donor atoms surrounding the metal centre quite far from the ideal tetrahedral geometry, as confirmed by continuous shape measures and by the τ<sub>4</sub> parameter. The intermolecular interactions at the solid state were investigated through the Hirshfeld surface analysis, which highlighted the presence of several non-classical hydrogen bonds involving the tetrafluoroborate anion. The electronic structure of the crystal was modelled using plane-wave DFT methods. The computed band gap is around 2.8 eV and separates a metal-centred valence band from a ligand-centred conduction band. NMR spectroscopy indicated the fluxional behaviour of the complex in CDCl<sub>3</sub> solution. The geometry of the compound in the presence of chloroform as implicit solvent was simulated by means of DFT calculations, together with possible mechanisms related to the fluxionality. The reversible dissociation of one of the pyrazole rings from the Cu(I) coordination sphere resulted in an accessible process.