By: Zhong-Zhi Wu a, Zu-En Huang a, *, Rui-Fang Cai a, Xi-Geng Zhou b, Zheng Xu b,
Xiao-Zeng You b, Xiao-Yun Huang c
a Department of Chemistry, Fudan University, Republic of China
Abstract
The trivalent lanthanide metallocenes Cp3Ln (Cp=CsHs, Ln= Dy or Yb) react with thiols, HSR (R=CH2CH2CH 3 or CH2CH2CH2CH 3) to give the dimeric complexes [Cp2Ln(~-SR)] z (R =CH2CH2CH3; Ln = Dy (1) or Yb (2)) (R = CH2CH2CH2CH3; Ln = Dy (3) or Yb (4)) in tetrahydrofuran at room temperature. They have been characterized by elemental analysis and mass spectroscopy or ~ H NMR spectra, indicating that they are dimers bridged through the sulphide atoms of thiolate ligands. Crystals of 4 are monoclinic, of space group P2j/a with a = 8.928(3), b = 17.620(7) and c = 9.208(4) A, /3 = 103.94(3) °, V = 1405.8(9) ,~3, Z = 2 and D c = 1.85 g cm 3. The structure was refined by the full-matrix least-squares method to a conventional R factor of 0.039, for 1868 data with I > 3o-(1). The Yb2S 2 unit is planar, and the geometry about the ytterbium atom is pseudotetrahedral although the geometry is pyramid at sulfur so that the n-butyl groups are anti relative to the Yb2S 2 ring. The average Y-C(Cp) and Yb-S bond distances are
2.59(1) and 2.708(3) ,~ respectively. It was found that these complexes are thermally unstable and tend to decompose into CP3Ln species upon heating.
Keywords: Dysprosium; Ytterbium; Cyclopentadienyl; Thiolate; Crystal structure
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The trivalent lanthanide metallocenes Cp3Ln (Cp=CsHs, Ln= Dy or Yb) react with thiols, HSR (R=CH2CH2CH 3 or CH2CH2CH2CH 3) to give the dimeric complexes [Cp2Ln(~-SR)] z (R =CH2CH2CH3; Ln = Dy (1) or Yb (2)) (R = CH2CH2CH2CH3; Ln = Dy (3) or Yb (4)) in tetrahydrofuran at room temperature. They have been characterized by elemental analysis and mass spectroscopy or ~ H NMR spectra, indicating that they are dimers bridged through the sulphide atoms of thiolate ligands. Crystals of 4 are monoclinic, of space group P2j/a with a = 8.928(3), b = 17.620(7) and c = 9.208(4) A, /3 = 103.94(3) °, V = 1405.8(9) ,~3, Z = 2 and D c = 1.85 g cm 3. The structure was refined by the full-matrix least-squares method to a conventional R factor of 0.039, for 1868 data with I > 3o-(1). The Yb2S 2 unit is planar, and the geometry about the ytterbium atom is pseudotetrahedral although the geometry is pyramid at sulfur so that the n-butyl groups are anti relative to the Yb2S 2 ring. The average Y-C(Cp) and Yb-S bond distances are
2.59(1) and 2.708(3) ,~ respectively. It was found that these complexes are thermally unstable and tend to decompose into CP3Ln species upon heating.
Keywords: Dysprosium; Ytterbium; Cyclopentadienyl; Thiolate; Crystal structure
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