Ni Oxidation State and Ligand Saturation Impact on the Capability of Octaazamacrocyclic Complexes to Bind and Reduce CO2 |
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Authors: | Barbora Vé nosová ,Ingrid Jelemenská ,Jozef Kož í š ek,Peter Rapta,Michal Zalibera,Michal Novotný ,Vladimir B. Arion,Luká š Buč inský |
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Abstract: | Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO2. In the first complex 1[NiIIL]0, the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second 1[NiIILH]2+ 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-CCO2 bond and the oxidation state of the central Ni atom. It was found that in the [NiLH] complex, the central atom is reduced to Ni0 and/or NiI and is thus able to bind CO2 via a single σ bond. In addition, the two-electron reduced 3[NiL]2− species also shows an affinity forwards CO2. |
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Keywords: | DFT nickel complexes CO2 reduction CO2 fixation CO2 catalysis domain averaged fermi holes bonding analysis QTAIM MPA |
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