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Reactions of ClF 3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates
Author(s) -
Scheibe Benjamin,
Karttunen Antti J.,
Kraus Florian
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000908
Subject(s) - chemistry , crystallography , raman spectroscopy , transition metal , crystal structure , ionic bonding , metal , covalent bond , single crystal , atom (system on chip) , inorganic chemistry , ion , catalysis , physics , organic chemistry , computer science , embedded system , optics , biochemistry
Compounds containing the dioxychloronium cation, [ClO 2 ] + , were obtained from reactions of ClF 3 with various oxides such as TiO 2 , MoO 3 , Re 2 O 7 , SnO, P 2 O 5 , As 2 O 5 , and Nb metal, as the latter contained oxide as an impurity. Partial hydrolysis of [ClF 2 ][IrF 6 ] led to the formation of [ClO 2 ][IrF 6 ]. The crystal structures of the compounds were determined by single‐crystal X‐ray diffraction, which showed that depending on the starting material [ClO 2 ] + salts with the fluoridometallate anions [TiF 3/2 F 3/1 ] 2 ] − , [Nb 3 F 16 ] − , [IrF 6 ] − , [SnF 2/2 F 4/1 ] − [PF 6 ] − , and [AsF 6 ] − , or with the oxidofluoridometallate anions [Mo 3 O 3 F 13 ] − and [Re 3 O 6 F 10 ] − , were obtained. Bent [ClO 2 ] + cations with short Cl ⋅ ⋅ ⋅ μ−F contacts of surrounding F atoms of the anions with the Cl atom are present in the crystal structures, leading to coordination numbers of 2+4 or 2+6 for the Cl atom. Various structural motifs are observed, which range from molecular, columnar, ladder‐like, to layer and framework structures. The salts were furthermore characterized by Raman spectroscopy and solid‐state quantum‐chemical calculations. Covalent Cl−O bonds and ionic Cl ⋅ ⋅ ⋅ μ−F interactions are indicated by the calculations.