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 language | English |
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Pages (from-to) | 4483-4496 |
Number of pages | 14 |
Journal | European Journal of Inorganic Chemistry |
Volume | 2020 |
Issue number | 47 |
Early online date | 5 Nov 2020 |
DOIs | |
Publication status | Published - 20 Dec 2020 |
MoE publication type | A1 Journal article-refereed |
Keywords
- Difluorochloronium(III) cation
- Chlorine trifluoride
- Fluorine chemistry
- Single‐
- crystal X‐
- ray diffraction
- ELECTRONIC-STRUCTURE CALCULATIONS
- FLUORIDE CRYSTAL-STRUCTURES
- BASIS-SETS
- CONFIGURATION ENERGIES
- INTERATOMIC DISTANCES
- IONS
- COMPLEXES
- VALENCE
- PROGRAM
- PAIR
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Dive into the research topics of 'Difluorochloronium(III) Fluoridometallates - from Molecular Building Blocks to (Helical) Chains'. Together they form a unique fingerprint.Datasets
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CSD 2008585: Experimental Crystal Structure Determination
Scheibe, B. (Creator), Haiges, R. (Creator), Ivlev, S. I. (Creator), Karttunen, A. (Creator), Müller, U. (Creator), Christe, K. O. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
Dataset
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CSD 2008579: Experimental Crystal Structure Determination
Scheibe, B. (Creator), Haiges, R. (Creator), Ivlev, S. I. (Creator), Karttunen, A. (Creator), Müller, U. (Creator), Christe, K. O. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
DOI: 10.25505/fiz.icsd.cc25f2wl
Dataset
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CSD 2008578: Experimental Crystal Structure Determination
Scheibe, B. (Creator), Haiges, R. (Creator), Ivlev, S. I. (Creator), Karttunen, A. (Creator), Müller, U. (Creator), Christe, K. O. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
DOI: 10.25505/fiz.icsd.cc25f2vk
Dataset