The electron density distribution of the complex monoanion Cu(CF3)4 in (Bu4N)[Cu(CF3)4] has been studied by high-resolution X-ray single-crystal diffraction and augmented with theoretical calculations. The study finds that the central copper bears an atomic charge of close to +1, while the occupancy of its dx2-y2 orbital is only 1.26. Using topological analysis combined with theoretical calculations, the depopulation of dx2-y2 is shown to be due to significant covalency in the Cu-C bonds. The combination of the monovalent picture and the covalency is interpreted as a confirmation of an inverted ligand field.

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF3)4- / C. Gao, G. Macetti, J. Overgaard. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 58:3(2019 Jan 15), pp. 2133-2139. [10.1021/acs.inorgchem.8b03226]

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF3)4-

G. Macetti
Secondo
;
2019

Abstract

The electron density distribution of the complex monoanion Cu(CF3)4 in (Bu4N)[Cu(CF3)4] has been studied by high-resolution X-ray single-crystal diffraction and augmented with theoretical calculations. The study finds that the central copper bears an atomic charge of close to +1, while the occupancy of its dx2-y2 orbital is only 1.26. Using topological analysis combined with theoretical calculations, the depopulation of dx2-y2 is shown to be due to significant covalency in the Cu-C bonds. The combination of the monovalent picture and the covalency is interpreted as a confirmation of an inverted ligand field.
Electron density; topological analysis; inverted ligand field; oxidation state
Settore CHIM/02 - Chimica Fisica
Settore CHIM/03 - Chimica Generale e Inorganica
15-gen-2019
Article (author)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/971202
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