Bulletin of the Korean Chemical Society

  • 제17권1호
  • /
  • Pages.46-50
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  • 1996
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Electron Microscopy and Magnetic Properties of Tetra(n-butyl) ammonium salts of $[Ni(dmbit)_2]^1- (dmbit^2-:C_7H_2S_5$:2-thiobenzo[d]-1,3-dithiole-5,6-dithiolate;$dmbbip^{2-}:C_{12}H_{16}S_4$:1,2-bis(isopropylthio)benzene-4,5-dithiolat

  • 발행 : 19960100
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초록

Monoanionic nickel(Ⅲ) complexes, [Ni(dmbit)2]1- and [Ni(dmbbip)2]1- where dmbit2- and dmbbip2- denote 2-thiobenzo[d]-1,3-dithiole-5,6-dithiolate and 1,2-bis(isopropylthio)benzen-4,5-dithiolate, respectively, have been synthesized by the iodine oxidation of dianionic complexes. In the scanning electron microscopic(SEM) images, these complexes show the well-grown two-dimensional layered structures which are clearly comparable to the dianionic ones with three-dimensional structures. Magnetic susceptibilities of nickel(Ⅲ)complexes are fitted well with the two-dimensional Heisenberg antiferromagnet model of S=1/2 system resulting in the spin-exchange parameters (|J|/k) of 11.4 K and 0.45 K, respectively. The weaker magnetic interaction in [Ni(dmbbip)2]1- is resulted from the bulky isopropyl groups on the periphery of dmbbip ligand. EPR measurements for [Ni(dmbit)2]1- give the signal with axial symmetry and the anisotropic g-values for low-spin nickel(Ⅲ) (g//=2.158, g =2.030,gav=2.074 at 300 K; g//=2.162, g =2.038, gav=2.080 at 77 K). It is therefore concluded that nickel(Ⅱ) is oxidized to nickel(Ⅲ), rather than dmbit2- and dmbbip2- ligands are, by the iodine oxidation. The paramagnetic Ni(Ⅲ) would be located in the axial symmetry(D4h) with the electronic configuration of (dxz2dyz2dz22dxy1dx2-y20).

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참고문헌

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피인용 문헌

  1. Bis(quinoxaline‐dithiolato)nickel(III) Complexes [Bu4N][NiIII(6,7‐qdt)2] and [Ph4P]­[NiIII(Ph26,7‐qdt) vol.2015, pp.33, 1996, https://doi.org/10.1002/ejic.201500739