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End-On Bridging Dinitrogen Complex of Scandium

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b08456· OSTI ID:1473943
 [1];  [1];  [1];  [2];  [1];  [1]
  1. Univ. of California, Irvine, CA (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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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.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1473943
Report Number(s):
SAND--2018-10055J; 667860
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 42 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Single Electron Transfer to Diazomethane–Borane Adducts Prompts C−H Bond Activations journal October 2019
Single Electron Transfer to Diazomethane-Borane Adducts Prompts C−H Bond Activations journal October 2019
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
Addition reactions and diazomethane capture by the intramolecular P–O–B FLP: t Bu 2 POBcat journal January 2020

Figures / Tables (4)

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Figure 3(p. 3)figure Figure 3
Scheme 1(p. 3)figure Scheme 1

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