Organolanthanoids XIX. The X-ray crystal structures of di [μ-(acetato-O,O:O′)bis(diphenylphosphino-η5-cyclopentadienyl)ytterbium(III)] and di[μ-(acetato-O,O:O′)bis(η5-cyclopentadienyl)ytterbium(III)] - unexpected examples of formal nine coordination in lanthanoid organometallics

Glen B. Deacon, Gary D. Fallon, Bryan M. Gatehouse, Anna Rabinovich, Brian W. Skelton, Allan H. White

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Abstract

Treatment of bis(diphenylphosphinocyclopentadienyl)ytterbium(II) with mercury(II) acetate in tetrahydrofuran (THF) gave Yb(C5H4PPh2)2(O2CCH3) as a fractional (0.75) THF solvate. Crystallization from toluene gave the THF-free dimer [Ybη5-C5H4PPh2)2(μ-O2CCH3)]2, the structure of which was determined by X-ray crystallography (monoclinic; P21/n; a = 9.615(2), b = 13.665(5), and c = 23.209(9) A ̊; β = 91.47(3)°; Z = 2(dimers); R = 0.034 for 3996 "observed" data). Unexpectedly, the bridging acetate groups are unsymmetrically chelating to one ytterbium atom and bonded by one oxygen atom to the other, and each ytterbium atom is formally nine coordinate with two η5-C5H4PPh2 groups (CtYbz.sbnd;Ct, 130.7°; Ct = centroid), two oxygen atoms from one bridging acetate (Ybz.sbnd;O, 2.454(4), and 2.339(4) Å), and one (Ybz.sbnd;O, 2.282(4)Å) from the other. For comparison, the structure of YbCp2(O2CCH3) (Cp = cyclopentadienyl) was determined (orthorhombic; Pbam; a = 13.16(1), b = 12.98(1) and c = 13.376(4) Å; Z = 4 (dimers); R = 0.058 for 1745 "observed" data) and showed the presence of two crystallographically different acetate-bridged dimers (A and B) with some variation between their geometries. Again, ytterbium is nine coordinated with two η5-Cp groups (CtYbCt, 132.1° (A) or 123.3° (B)), two nearly symmetrically bonded oxygen atoms from one acetate (cf. Yb(C5H4PPh2)2(O2CCH3)) (Yb-0 2.38(1) and 2.39(1) Å (A) or 2.42(1) and 2.39(1) Å (B)) and one more tightly bound oxygen atom (YbO, 2.25(1) Å (A) or 2.28(1) Å (B)) from the other acetate.

Original languageEnglish
Pages (from-to)23-30
Number of pages8
JournalJournal of Organometallic Chemistry
Volume501
Issue number1-2
DOIs
Publication statusPublished - 4 Oct 1995

Keywords

  • Acetate
  • Cyclopentadienyl
  • X-ray structure
  • Ytterbium

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