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

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.

Photochemistry with ClF3 – An Access to [ClOF2]+ Salts

“…Triple‐zeta‐valence+polarization (TZVP) level basis sets were applied for all atoms. The basis sets were derived from the Karlsruhe def‐TZVP basis sets and were taken from previous studies (B, O, F, Cl, Ge, Sn, Sb, Os, Pt, Au, Pb) or are described in the Supporting Information (Cr, Pd, Rh) [22,23,100–106] . All calculations were carried out with the CRYSTAL17 program package [107] .…”

“…Salts containing [ClF 2 ] + cations were obtained if strong enough Lewis acids for fluoride anion abstraction from ClF 3 were formed as intermediates which then converted to stable fluorido(non)metallate anions such as [AuF 4 ] − or [ M F 6 ] − (see Figure 1). [22] These compounds contained bent [ClF 2 ] + cations with polarized‐covalent Cl−F bonds. However, the Cl atoms formed two additional longer contacts to F ligands of the complex anions and coordination numbers of 2+2 were regularly observed.…”

“… Overview of selected compounds obtained from reactions with ClF 3 , including those described in this work [9–24] …”

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…In all cases, salts containing the [ClO 2 ] + cation were obtained, as shown by single-crystal X-ray diffraction and Raman spectroscopy. Furthermore, the hydrolysis reaction of [57] All given equations are idealized and assume that ClO 2 F and/or ClF are the sole side-products in these reactions. ClO 2 F and ClF are themselves oxidizing and fluorinating agents, and depending on the reaction conditions, O 2 and Cl 2 might also be formed.…”

“…] rapidly deteriorated at room temperature and contact to the atmosphere. [57,59] After that, the reaction vessel was closed again and stored at room temperature for ten days, after which yellow crystals of were selected in the absence of air under dried, cooled perfluoropolyether (Galden HT270, Solvay, stored over molecular sieves 3 Å) and mounted on a MiTeGen loop. Intensity data of suitable crystals were recorded with a D8 Quest diffractometer (Bruker), an IPDS2, or an IPDS2T diffractometer (STOE).…”