End-On Bridging Dinitrogen Complex of Scandium
Abstract
The first (N=N)2- complex of a rare-earth metal with an end-on dinitrogen bridge, {K(crypt)}2{[(R2N)3Sc]2[μ-η1:η1-n2]} (crypt = 2.2.2-cryptand, R = SiMe3), has been isolated from the reduction of Sc(NR2)3 under dinitrogen at —35 °C and characterized by X-ray crystallography. The structure differs from the characteristic side-on structures previously observed for over 40 crystallographically-characterized rare-earth metal (N=N)2- complexes of formula [A2Ln(THF)x]2[μ-η2:η2-N2] (Ln = Sc, Y, and lanthanides; x = 0, 1; A = anionic ligand such as amide, cyclopentadienide, and aryloxide). The 1.221(3) Å N—N distance and the 1644 cm-1 Raman stretch are consistent with the presence of an (N=N)2- bridge. The observed paramagnetism of the complex by NMR spectroscopy and Evans method measurements is consistent with DFT calculations that suggest a triplet( 3A2) ground state in D3 symmetry involving two degenerate Sc—N2—Sc bonding orbitals. Upon brief exposure of the orange Sc3+ bridging dinitrogen complex to UV-light, photolysis to form the monomeric Sc2+ complex, [K(crypt)][Sc(NR2)3], was observed. Conversion of the Sc2+ complex to the SO3+ dinitrogen complex was not observed with this crypt system, but it did occur with the 18-crown-6 (crown) analog which formed {K(crown)}2{[(R2N)3Sc]2[μ-η1:η1-N2]}. This suggests the importance of the alkali metal chelating agent in the reversibility of dinitrogen bindingmore »
- Authors:
-
- Univ. of California, Irvine, CA (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1473943
- Report Number(s):
- SAND-2018-10055J
Journal ID: ISSN 0002-7863; 667860
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 42; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Woen, David H., Chen, Guo P., Ziller, Joseph W., Boyle, Timothy J., Furche, Filipp, and Evans, William J. End-On Bridging Dinitrogen Complex of Scandium. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b08456.
Woen, David H., Chen, Guo P., Ziller, Joseph W., Boyle, Timothy J., Furche, Filipp, & Evans, William J. End-On Bridging Dinitrogen Complex of Scandium. United States. doi:10.1021/jacs.7b08456.
Woen, David H., Chen, Guo P., Ziller, Joseph W., Boyle, Timothy J., Furche, Filipp, and Evans, William J. Thu .
"End-On Bridging Dinitrogen Complex of Scandium". United States. doi:10.1021/jacs.7b08456. https://www.osti.gov/servlets/purl/1473943.
@article{osti_1473943,
title = {End-On Bridging Dinitrogen Complex of Scandium},
author = {Woen, David H. and Chen, Guo P. and Ziller, Joseph W. and Boyle, Timothy J. and Furche, Filipp and Evans, William J.},
abstractNote = {The first (N=N)2- complex of a rare-earth metal with an end-on dinitrogen bridge, {K(crypt)}2{[(R2N)3Sc]2[μ-η1:η1-n2]} (crypt = 2.2.2-cryptand, R = SiMe3), has been isolated from the reduction of Sc(NR2)3 under dinitrogen at —35 °C and characterized by X-ray crystallography. The structure differs from the characteristic side-on structures previously observed for over 40 crystallographically-characterized rare-earth metal (N=N)2- complexes of formula [A2Ln(THF)x]2[μ-η2:η2-N2] (Ln = Sc, Y, and lanthanides; x = 0, 1; A = anionic ligand such as amide, cyclopentadienide, and aryloxide). The 1.221(3) Å N—N distance and the 1644 cm-1 Raman stretch are consistent with the presence of an (N=N)2- bridge. The observed paramagnetism of the complex by NMR spectroscopy and Evans method measurements is consistent with DFT calculations that suggest a triplet( 3A2) ground state in D3 symmetry involving two degenerate Sc—N2—Sc bonding orbitals. Upon brief exposure of the orange Sc3+ bridging dinitrogen complex to UV-light, photolysis to form the monomeric Sc2+ complex, [K(crypt)][Sc(NR2)3], was observed. Conversion of the Sc2+ complex to the SO3+ dinitrogen complex was not observed with this crypt system, but it did occur with the 18-crown-6 (crown) analog which formed {K(crown)}2{[(R2N)3Sc]2[μ-η1:η1-N2]}. This suggests the importance of the alkali metal chelating agent in the reversibility of dinitrogen binding in this scandium system.},
doi = {10.1021/jacs.7b08456},
journal = {Journal of the American Chemical Society},
number = 42,
volume = 139,
place = {United States},
year = {2017},
month = {9}
}
Web of Science
Figures / Tables:

Works referencing / citing this record:
CCDC 1567376: Experimental Crystal Structure Determination: ACUJOA : bis((4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)-potassium) (μ-dinitrogen)-hexakis(bis(trimethylsilyl)amide)-di-scandium diethyl ether solvate
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Isolation of reactive Ln( ii ) complexes with C 5 H 4 Me ligands (Cp Me ) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-Cp Me )K(18-crown-6)][Cp Me 3 Ln II ] (Ln = Tb, Ho)
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Single Electron Transfer to Diazomethane-Borane Adducts Prompts C−H Bond Activations
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Addition reactions and diazomethane capture by the intramolecular P–O–B FLP: t Bu 2 POBcat
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Single Electron Transfer to Diazomethane-Borane Adducts Prompts C−H Bond Activations
journal, October 2019
- Cao, Levy L.; Zhou, Jiliang; Qu, Zheng-Wang
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Isolation of reactive Ln( ii ) complexes with C 5 H 4 Me ligands (Cp Me ) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-Cp Me )K(18-crown-6)][Cp Me 3 Ln II ] (Ln = Tb, Ho)
journal, January 2018
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Addition reactions and diazomethane capture by the intramolecular P–O–B FLP: t Bu 2 POBcat
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Single Electron Transfer to Diazomethane–Borane Adducts Prompts C−H Bond Activations
journal, October 2019
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- Angewandte Chemie, Vol. 131, Issue 51
Figures / Tables found in this record: