Difluorochloronium(III) Fluoridometallates - from Molecular Building Blocks to (Helical) Chains

Benjamin Scheibe, Ralf Haiges, Sergei I. Ivlev, Antti J. Karttunen, Ulrich Müller, Karl O. Christe, Florian Kraus*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

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Abstract

Difluorochloronium(III) compounds were synthesized from the reaction of metal powders (Ru, Os, Ir, Au), metal fluorides (NbF5, SbF3, BiF5) or a metal chloride (TaCl5) with excess liquid chlorine trifluoride. The compounds ClF2[AuF4], ClF2[MF6] (M = Nb, Ta, Ru, Os, Ir, Sb, Bi) and ClF2[Ta2F11] were obtained in crystalline form and their crystal structures were determined by single-crystal X-ray diffraction. The ClF2+ cations in the investigated compounds are bent, containing two strong, short, mainly covalent Cl-F bonds and two sterically active, free valence electron pairs in a pseudo-tetrahedral arrangement. The coordination around the Cl atom is extended by two highly ionic, long fluorine bridges to neighboring fluoridometallate anions, resulting in a total coordination number of six. The crystal structures vary among the ClF2+ compounds and range from molecular building blocks, such as dimeric (ClF2[AuF4])(2) and (ClF2[Ta2F11])(2), to chains, some of which being helical, as in ClF2[MF6], (M = Nb, Ta, Ru, Os, Ir, Sb, Bi). Quantum-chemical solid-state and gas-phase calculations were carried out to elucidate the bonding within the ClF2+ cations and their interactions with the bridging F atoms.

Original languageEnglish
Pages (from-to)4483-4496
Number of pages14
JournalEuropean Journal of Inorganic Chemistry
Volume2020
Issue number47
Early online date5 Nov 2020
DOIs
Publication statusPublished - 20 Dec 2020
MoE publication typeA1 Journal article-refereed

Keywords

  • Difluorochloronium(III) cation
  • Chlorine trifluoride
  • Fluorine chemistry
  • Single&#8208
  • crystal X&#8208
  • ray diffraction
  • ELECTRONIC-STRUCTURE CALCULATIONS
  • FLUORIDE CRYSTAL-STRUCTURES
  • BASIS-SETS
  • CONFIGURATION ENERGIES
  • INTERATOMIC DISTANCES
  • IONS
  • COMPLEXES
  • VALENCE
  • PROGRAM
  • PAIR

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