Isolation of Dysprosium and Yttrium Complexes of a Three-Electron Reduction Product in the Activation of Dinitrogen, the N23- Radical - École polytechnique Access content directly
Journal Articles Journal of the American Chemical Society Year : 2009

Isolation of Dysprosium and Yttrium Complexes of a Three-Electron Reduction Product in the Activation of Dinitrogen, the N23- Radical

W.J. Evans
  • Function : Author
Ming Fang
  • Function : Author
Filipp Furche
  • Function : Author
J.W. Ziller
  • Function : Author
R.M. Hoekstra
  • Function : Author
J.I. Zink
  • Function : Author

Abstract

DyI2 reacts with 2 equiv of KOAr (OAr ) OC6H3(CMe3)2-2,6) under nitrogen to form not only the (N2)2- complex, [(ArO)2(THF)2Dy]2(μ-η2:η2-N2), 1, but also complexes of similar formula with an added potassium ion, [(ArO)2(THF)Dy]2(μ-η2:η2-N2)[K(THF)6], 2, and [(ArO)2(THF)Dy]2(μ3-η2:η2:η2-N2)K(THF), 3. The 1.396(7) and 1.402(7) Å N-N bond distances in 2 and 3, respectively, are consistent with an (N2)3- ligand, but the high magnetic moment of 4f9 Dy3+ precluded definitive identification. The Y[N(SiMe3)2]3/K reduction system was used to synthesize yttrium analogues of 2 and 3, {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2- N2)[K(THF)6] and {[(Me3Si)2N]2(THF)Y}2(μ3-η2:η2:η2-N2)K, that had similar N-N distances and allowed full characterization. EPR, Raman, and DFT studies are all consistent with the presence of (N2)3- in these complexes. 15N analogues were also prepared to confirm the spectroscopic assignments. The DFT studies suggest that the unpaired electron is localized primarily in a dinitrogen π orbital isolated spatially, energetically, and by symmetry from the metal orbitals.
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Dates and versions

hal-00843063 , version 1 (10-07-2013)

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Gaël Zucchi, W.J. Evans, Ming Fang, Filipp Furche, J.W. Ziller, et al.. Isolation of Dysprosium and Yttrium Complexes of a Three-Electron Reduction Product in the Activation of Dinitrogen, the N23- Radical. Journal of the American Chemical Society, 2009, 131, pp.11191. ⟨10.1021/ja9036753⟩. ⟨hal-00843063⟩
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