Electron Localization in a Mixed-Valence Diniobium Benzene Complex
Abstract
Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]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)NtBu]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.
- Authors:
-
- Univ. of California, Berkeley, CA (United States)
- Centre National de la Recherche Scientifique (CNRS), Palaiseau (France)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. College London, London (United Kingdom)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1321749
- Alternate Identifier(s):
- OSTI ID: 1214426
- Report Number(s):
- LA-UR-14-27537
Journal ID: ISSN 2041-6520
- Grant/Contract Number:
- AC52-06NA25396; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry; Niobium Benzene Comples
Citation Formats
Gianetti, Thomas L., Nocton, Gregory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. D., Kozimor, Stosh Anthony, Shuh, David K., Tyliszczak, Tolek, Bergman, Robert G., and Arnold, John. Electron Localization in a Mixed-Valence Diniobium Benzene Complex. United States: N. p., 2014.
Web. doi:10.1039/C4SC02705A.
Gianetti, Thomas L., Nocton, Gregory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. D., Kozimor, Stosh Anthony, Shuh, David K., Tyliszczak, Tolek, Bergman, Robert G., & Arnold, John. Electron Localization in a Mixed-Valence Diniobium Benzene Complex. United States. https://doi.org/10.1039/C4SC02705A
Gianetti, Thomas L., Nocton, Gregory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. D., Kozimor, Stosh Anthony, Shuh, David K., Tyliszczak, Tolek, Bergman, Robert G., and Arnold, John. Tue .
"Electron Localization in a Mixed-Valence Diniobium Benzene Complex". United States. https://doi.org/10.1039/C4SC02705A. https://www.osti.gov/servlets/purl/1321749.
@article{osti_1321749,
title = {Electron Localization in a Mixed-Valence Diniobium Benzene Complex},
author = {Gianetti, Thomas L. and Nocton, Gregory and Minasian, Stefan G. and Kaltsoyannis, Nikolas and Kilcoyne, A. L. D. and Kozimor, Stosh Anthony and Shuh, David K. and Tyliszczak, Tolek and Bergman, Robert G. and Arnold, John},
abstractNote = {Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]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)NtBu]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.},
doi = {10.1039/C4SC02705A},
journal = {Chemical Science},
number = 2,
volume = 6,
place = {United States},
year = {Tue Nov 11 00:00:00 EST 2014},
month = {Tue Nov 11 00:00:00 EST 2014}
}
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