Synthesis and characterization of zirconium pentafluorophenyl complexes: X-ray crystal structures of [ZrCl2(C6F5)42-] and [ZrF2(C6F5)53-]

Melissa J. Nelsen, Gregory S. Girolami

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Treatment of ZrCl4 with LiC6F5, followed by addition of 1,4,7,10-tetraoxacyclododecane (12-crown-4) or N,N,N′,N′-tetramethylethylenediamine (tmed), leads to the isolation of two pentafluorophenylzirconate complexes: [Li(12-crown-4)2]2[ZrCl2(C6F 5)4] (1) and [Li(tmed)2][Li(tmed)]2[ZrF2(C6F 5)5] (2). The presence of Zr-F groups in the latter compound shows that C-F bond activation has occurred. The anion in the former complex adopts an octahedral structure owing to the π-donor character of the chloride ligands, whereas the anion in the latter adopts a regular pentagonal bipyramidal structure. The lithium atoms in 1 are not interacting with the anion, whereas two of the lithium atoms in 2 are involved in LiF interactions with fluorine atoms in the anion. Selected bond distances and angles for 1: Zr-C=2.478(5)-2.510(5), Zr-Cl=2.409(5), 2.435(5) Å, C-Zr-C(cis)=77.9-106.9(2), C-Zr-C(trans)=161.1, 169.1(2), Cl-Zr-Cl=166.7(2)°. Selected bond distances and angles for 2: Zr-C=2.432-2.449(8), Zr-F=1.986(4), LiF=1.73(2)-2.50(2) Å, C-Zr-C(cis)=69.6-73.3, F-Zr-F=178.8(2)°. Crystal data for 1: monoclinic, space group P21/n, a=15.2288(14), b=17.328(2), c=24.013(2) Å, β=91.936(3)°, V=6333(1) Å3, Z=4, wR2=0.2985 for 7801 reflections and 722 parameters. Crystal data for 2: monoclinic, space group P21/n, a=11.6143(5), b=29.6561(9), c=20.4427(8) Å, β=103.266(1)°, V=6853.3(4) Å3, Z=4, wR2=0.1822 for 8762 reflections and 759 parameters.

Original languageEnglish (US)
Pages (from-to)275-284
Number of pages10
JournalJournal of Organometallic Chemistry
Issue number2
StatePublished - Aug 15 1999


  • Carbon-fluorine bond activation
  • Group 4
  • Pentafluorophenyl
  • Seven-coordination
  • Zirconium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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