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

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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2020-12-20

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Department of Chemistry and Materials Science

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en

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14

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European Journal of Inorganic Chemistry, Volume 2020, issue 47, pp. 4483-4496

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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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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DOI

10.1002/ejic.202000845

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

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https://urn.fi/URN:NBN:fi:aalto-202101251558

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[article-cris] Kemian tekniikan korkeakoulu / CHEM