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

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Journal ISSN
Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2020-12-20
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Mcode
Degree programme
Language
en
Pages
14
4483-4496
Series
European Journal of Inorganic Chemistry, Volume 2020, issue 47
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.
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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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Citation
Scheibe , B , Haiges , R , Ivlev , S I , Karttunen , A J , Müller , U , Christe , K O & Kraus , F 2020 , ' Difluorochloronium(III) Fluoridometallates - from Molecular Building Blocks to (Helical) Chains ' , European Journal of Inorganic Chemistry , vol. 2020 , no. 47 , pp. 4483-4496 . https://doi.org/10.1002/ejic.202000845