Compounds containing the dioxychloronium cation, [ClO₂]⁺, were obtained from reactions of ClF₃ with various oxides such as TiO₂, MoO₃, Re₂O₇, SnO, P₂O₅, As₂O₅, and Nb metal, as the latter contained oxide as an impurity. Partial hydrolysis of [ClF₂][IrF₆] led to the formation of [ClO₂][IrF₆]. The crystal structures of the compounds were determined by single‐crystal X‐ray diffraction, which showed that depending on the starting material [ClO₂]⁺ salts with the fluoridometallate anions [TiF_3/2F_3/1]₂]⁻, [Nb₃F₁₆]⁻, [IrF₆]⁻, [SnF_2/2F_4/1]⁻ [PF₆]⁻, and [AsF₆]⁻, or with the oxidofluoridometallate anions [Mo₃O₃F₁₃]⁻ and [Re₃O₆F₁₀]⁻, were obtained. Bent [ClO₂]⁺ 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.

中文翻译：

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ClF3与主要基团和过渡金属氧化物的反应：获得二氧氯鎓（V）氟代金属盐和氧代氟代金属盐

通过ClF ₃与各种氧化物（例如TiO ₂，MoO ₃，Re ₂ O ₇，SnO，P ₂ O ₅，As ₂ O ₅和Nb金属）的反应获得含有二氧氯鎓阳离子[ClO ₂ ] ^+的化合物。，因为后者包含氧化物作为杂质。[ClF ₂ ] [IrF ₆ ]的部分水解导致[ClO ₂ ] [IrF ₆ ]的形成。通过单晶X射线衍射确定化合物的晶体结构，结果表明取决于原料[ClO ₂] ⁺与氟金属阴离子[TiF _3/2 F _3/1 ] ₂ ] ^-，[Nb ₃ F ₁₆ ] ^-，[IrF ₆ ] ^-，[SnF _2/2 F _4/1 ] ^- [PF ₆ ]形成的盐^-和[AsF ₆ ] ^-或含氧氟金属阴离子[Mo ₃ O ₃ F ₁₃ ] ^-和[Re ₃ O ₆ F ₁₀ ] ^-，已获得。晶体结构中存在与阴离子周围的F原子具有短Cl⋅⋅⋅μ-F接触的弯曲[ClO ₂ ] ⁺阳离子，导致Cl的配位数为2 + 4或2 + 6原子。观察到各种结构基序，范围从分子，柱状，梯形到层和框架结构。通过拉曼光谱和固态量子化学计算进一步表征了这些盐。计算表明共价Cl-O键和离子Cl-⋅⋅μ-F相互作用。