Ni Oxidation State and Ligand Saturation Impact on the Capability of Octaazamacrocyclic Complexes to Bind and Reduce CO 2

Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO . In the first complex [ ] , the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second [ ] one, the macrocyc...

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Bibliographic Details
Published in:Molecules (Basel, Switzerland) Switzerland), 2021-07, Vol.26 (14)
Main Authors: Vénosová, Barbora, Jelemenská, Ingrid, Kožíšek, Jozef, Rapta, Peter, Zalibera, Michal, Novotný, Michal, Arion, Vladimir B, Bučinský, Lukáš
Format: Article
Language:English
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Summary:Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO . In the first complex [ ] , the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second [ ] one, the macrocycle is saturated with hydrogens. One and two-electron reductions are described using Mulliken population analysis, quantum theory of atoms in molecules, localized orbitals, and domain averaged fermi holes, including the characterization of the Ni-C bond and the oxidation state of the central Ni atom. It was found that in the [ ] complex, the central atom is reduced to Ni and/or Ni and is thus able to bind CO via a single σ bond. In addition, the two-electron reduced [ ] species also shows an affinity forwards CO .
ISSN:1420-3049