skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electron localization in a mixed-valence diniobium benzene complex

Abstract

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 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 L 3,2-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:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [5];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States)
  2. Ecole Ploytechnique, Palaiseau (France)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. College London, London (United Kingdom)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS).
  6. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1321749
Alternate Identifier(s):
OSTI ID: 1214426
Report Number(s):
LA-UR-14-27537
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
AC02-05CH11231; AC52-06NA25396
Resource Type:
Journal Article: 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, Grégory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. David, Kozimor, Stosh A., 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, Grégory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. David, Kozimor, Stosh A., Shuh, David K., Tyliszczak, Tolek, Bergman, Robert G., & Arnold, John. Electron localization in a mixed-valence diniobium benzene complex. United States. doi:10.1039/C4SC02705A.
Gianetti, Thomas L., Nocton, Grégory, Minasian, Stefan G., Kaltsoyannis, Nikolas, Kilcoyne, A. L. David, Kozimor, Stosh A., Shuh, David K., Tyliszczak, Tolek, Bergman, Robert G., and Arnold, John. Tue . "Electron localization in a mixed-valence diniobium benzene complex". United States. doi: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, Grégory and Minasian, Stefan G. and Kaltsoyannis, Nikolas and Kilcoyne, A. L. David and Kozimor, Stosh A. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006