Arnold, John

Bergman, Robert G

Gianetti, Thomas L

Kaltsoyannis, Nikolas

Kilcoyne, A L David

Kozimor, Stosh A

Minasian, Stefan G

Nocton, Gregory

Shuh, David K

Tyliszczak, Tolek

Chemical Science

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N t Bu]2(μ-C6H6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C6F5)4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N t Bu]2(μ-C6H6)}{B(C6F5)4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex

Nocton, Grégory

Kilcoyne, AL David

eScholarship - University of California

Electron localization in a mixed-valence diniobium benzene complex

Gianetti, Thomas

Minasian, Stefan

Kozimor, A.

Shuh, David

Bergman, Robert

HAL-Polytechnique

The University of Manchester - Institutional Repository

One electron oxidation of a neutral diniobium benzene complex leads to a mixed-valence species. Single crystal X-ray diffraction, EPR, L3,2-edge XANES, and DFT indicate that the unpaired electron is localized on one metal center.</p

Electron localization in a mixed-valence diniobium benzene complex

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eScholarship - University of California

HAL-Polytechnique

The University of Manchester - Institutional Repository

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