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Issue 26, 2012
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Synthesis and electronic properties of a pentafluoroethyl-derivatized nickel pincer complex

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Abstract

The synthesis of a bis(amino)amide nickel pincer complex bearing a perfluoroethyl ligand was effected by reaction of the corresponding nickel chloride complex with cesium fluoride and trimethyl(pentafluoroethyl)silane. Electrochemical experiments revealed that the oxidation of the LNi–C2F5 complex occurs at the same potential as the LNi–Cl derivative, but reduction of the LNi–C2F5 complex occurs at slightly more positive potentials. The similarity of the electrochemical data was corroborated by density functional theory (DFT), which predicts that the energies of the HOMOs (HOMO = highest occupied molecular orbital) and LUMOs (LUMO = lowest unoccupied molecular orbital) of the LNi–C2F5 and LNi–Cl complexes are equal in magnitude. DFT also revealed that the HOMOs of the bis(amino)amide nickel pincer complexes are primarily ligand in character, while the LUMOs are predominantly metal in character, supporting redox-activity with this ligand.

Graphical abstract: Synthesis and electronic properties of a pentafluoroethyl-derivatized nickel pincer complex

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Publication details

The article was received on 18 Jan 2012, accepted on 12 Mar 2012 and first published on 14 Mar 2012


Article type: Paper
DOI: 10.1039/C2DT30131H
Citation: Dalton Trans., 2012,41, 7915-7919
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    Synthesis and electronic properties of a pentafluoroethyl-derivatized nickel pincer complex

    V. N. Madhira, P. Ren, O. Vechorkin, X. Hu and D. A. Vicic, Dalton Trans., 2012, 41, 7915
    DOI: 10.1039/C2DT30131H

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