Synthesis and characterization of LnF(HF)(BF4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy), and crystal structures of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3

Zoran Mazej, Evgeny Goreshnik, Kohei Hironaka, Yasushi Katayama, Rika Hagiwara

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Rare earth trifluorides (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) react with boron trifluoride in anhydrous hydrogen fluoride (aHF) at room temperature. Products were found to be only sparingly soluble in aHF where the solubility decreases from lanthanum to dysprosium. After an excess of BF 3 and aHF were pumped away at ambient temperature, LnF(HF)(BF 4)2 type of compounds were isolated. Single crystals of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3 were grown for 3-5 months from solutions of LnF3 (Ln = La, Pr) and Nd2O3 in aHF under pressure of BF3 (4 bar). Structures consist from the zig-zag [-Ln-F-Ln-] (Ln = Pr, Nd) chains connected via BF4 units and HF molecules into tridimensional network. The Ln-F(Ln) distan-ces are significantly shorter [2.2489(6) Å for Pr and 2.234(1) Å for Nd] than Ln-F(BF4-) and Ln-F(HF) ones [Pr: 2.461(4)-2.528(5) Å, Nd : 2.446(7)-2.511(9) Å]. In La(BF4)3, the lanthanum atoms are coordinated by nine fluorine atoms with seven shorter La-F distances [2.410(2)-2.485(2) Å] and two elongated ones [2.600(2) Å]. The vibrational spectra of isolated rare earth tetrafluoroborates show strong deviations of the [BF4] - anions from ideal 7d symmetry. Because of the strong cation-anion interactions, the splittings of the anion vibrational modes are observed indicating rather covalent character of the bonding between LnF 3 and BF3.

Original languageEnglish
Pages (from-to)2309-2315
Number of pages7
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume635
Issue number13-14
DOIs
Publication statusPublished - 2009 Nov
Externally publishedYes

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Hydrofluoric Acid
Crystal structure
Anions
Lanthanum
Rare earths
Dysprosium
Atoms
Fluorine
Vibrational spectra
Cations
Solubility
Single crystals
Temperature
Molecules

Keywords

  • Boron
  • Coordination chemistry
  • Fluorine
  • Rare earth compounds
  • Vibrational spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and characterization of LnF(HF)(BF4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy), and crystal structures of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3. / Mazej, Zoran; Goreshnik, Evgeny; Hironaka, Kohei; Katayama, Yasushi; Hagiwara, Rika.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 635, No. 13-14, 11.2009, p. 2309-2315.

Research output: Contribution to journalArticle

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title = "Synthesis and characterization of LnF(HF)(BF4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy), and crystal structures of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3",
abstract = "Rare earth trifluorides (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) react with boron trifluoride in anhydrous hydrogen fluoride (aHF) at room temperature. Products were found to be only sparingly soluble in aHF where the solubility decreases from lanthanum to dysprosium. After an excess of BF 3 and aHF were pumped away at ambient temperature, LnF(HF)(BF 4)2 type of compounds were isolated. Single crystals of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3 were grown for 3-5 months from solutions of LnF3 (Ln = La, Pr) and Nd2O3 in aHF under pressure of BF3 (4 bar). Structures consist from the zig-zag [-Ln-F-Ln-] (Ln = Pr, Nd) chains connected via BF4 units and HF molecules into tridimensional network. The Ln-F(Ln) distan-ces are significantly shorter [2.2489(6) {\AA} for Pr and 2.234(1) {\AA} for Nd] than Ln-F(BF4-) and Ln-F(HF) ones [Pr: 2.461(4)-2.528(5) {\AA}, Nd : 2.446(7)-2.511(9) {\AA}]. In La(BF4)3, the lanthanum atoms are coordinated by nine fluorine atoms with seven shorter La-F distances [2.410(2)-2.485(2) {\AA}] and two elongated ones [2.600(2) {\AA}]. The vibrational spectra of isolated rare earth tetrafluoroborates show strong deviations of the [BF4] - anions from ideal 7d symmetry. Because of the strong cation-anion interactions, the splittings of the anion vibrational modes are observed indicating rather covalent character of the bonding between LnF 3 and BF3.",
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T1 - Synthesis and characterization of LnF(HF)(BF4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy), and crystal structures of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3

AU - Mazej, Zoran

AU - Goreshnik, Evgeny

AU - Hironaka, Kohei

AU - Katayama, Yasushi

AU - Hagiwara, Rika

PY - 2009/11

Y1 - 2009/11

N2 - Rare earth trifluorides (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) react with boron trifluoride in anhydrous hydrogen fluoride (aHF) at room temperature. Products were found to be only sparingly soluble in aHF where the solubility decreases from lanthanum to dysprosium. After an excess of BF 3 and aHF were pumped away at ambient temperature, LnF(HF)(BF 4)2 type of compounds were isolated. Single crystals of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3 were grown for 3-5 months from solutions of LnF3 (Ln = La, Pr) and Nd2O3 in aHF under pressure of BF3 (4 bar). Structures consist from the zig-zag [-Ln-F-Ln-] (Ln = Pr, Nd) chains connected via BF4 units and HF molecules into tridimensional network. The Ln-F(Ln) distan-ces are significantly shorter [2.2489(6) Å for Pr and 2.234(1) Å for Nd] than Ln-F(BF4-) and Ln-F(HF) ones [Pr: 2.461(4)-2.528(5) Å, Nd : 2.446(7)-2.511(9) Å]. In La(BF4)3, the lanthanum atoms are coordinated by nine fluorine atoms with seven shorter La-F distances [2.410(2)-2.485(2) Å] and two elongated ones [2.600(2) Å]. The vibrational spectra of isolated rare earth tetrafluoroborates show strong deviations of the [BF4] - anions from ideal 7d symmetry. Because of the strong cation-anion interactions, the splittings of the anion vibrational modes are observed indicating rather covalent character of the bonding between LnF 3 and BF3.

AB - Rare earth trifluorides (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) react with boron trifluoride in anhydrous hydrogen fluoride (aHF) at room temperature. Products were found to be only sparingly soluble in aHF where the solubility decreases from lanthanum to dysprosium. After an excess of BF 3 and aHF were pumped away at ambient temperature, LnF(HF)(BF 4)2 type of compounds were isolated. Single crystals of LnF(HF)(BF4)2 (Ln = Pr, Nd) and La(BF4) 3 were grown for 3-5 months from solutions of LnF3 (Ln = La, Pr) and Nd2O3 in aHF under pressure of BF3 (4 bar). Structures consist from the zig-zag [-Ln-F-Ln-] (Ln = Pr, Nd) chains connected via BF4 units and HF molecules into tridimensional network. The Ln-F(Ln) distan-ces are significantly shorter [2.2489(6) Å for Pr and 2.234(1) Å for Nd] than Ln-F(BF4-) and Ln-F(HF) ones [Pr: 2.461(4)-2.528(5) Å, Nd : 2.446(7)-2.511(9) Å]. In La(BF4)3, the lanthanum atoms are coordinated by nine fluorine atoms with seven shorter La-F distances [2.410(2)-2.485(2) Å] and two elongated ones [2.600(2) Å]. The vibrational spectra of isolated rare earth tetrafluoroborates show strong deviations of the [BF4] - anions from ideal 7d symmetry. Because of the strong cation-anion interactions, the splittings of the anion vibrational modes are observed indicating rather covalent character of the bonding between LnF 3 and BF3.

KW - Boron

KW - Coordination chemistry

KW - Fluorine

KW - Rare earth compounds

KW - Vibrational spectroscopy

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