Соли диоксигенила

Соли диоксигенила (диоксигенильные соединения) — соли катиона кислорода O₂⁺.

Получение

Первое соединение этого типа было получено в 1962 году реакцией кислорода с гексафторидом платины:

{\mathsf {O_{2}+PtF_{6}\rightarrow O_{2}^{+}PtF_{6}^{-}}}

Обычными способами получения являются реакция диоксидифторида с фторидами элементов или физическое воздействие, активирующее смесь фторида металла, фтора и кислорода (УФ-облучение, электроразряд, давление с нагреванием).

Строение

Длина связи O-O в катионе (0,1123 нм) меньше, чем у молекулы кислорода. Катион содержит один неспаренный электрон, поэтому все соли парамагнитны. Для стабилизации соли, анион должен быть стабилен и устойчив к окислению. Известны соли с анионами MF₆^- (где М = Au, Pt, Ru, Rh, Sb, As, P), BF₄^-, MF₆^2- (где М = Mn, Ni, Pd).

Физические и химические свойства

При нагревании разлагаются до кислорода, фтора и фторида металла. Являются сильными фторокислителями. С органическими веществами реагируют со взрывом и воспламенением. Могут окислять ксенон при комнатной температуре.

{\mathsf {O_{2}PtF_{6}+Xe\rightarrow XePtF_{6}+O_{2}\uparrow }}

Диоксигенилфторид (O₂F) со взрывом реагирует с ксеноновой кислотой (H₄XeO₆):

{\mathsf {2O_{2}F+H_{4}XeO_{6}\rightarrow XeF_{2}+H_{2}O+4O_{2}\uparrow }}

Имеет димер O₄F₂, отличающийся менее выраженными свойствами и меньшей стабильностью

Литература

Химическая энциклопедия / Редкол.: Кнунянц И.Л. и др.. — М.: Советская энциклопедия, 1990. — Т. 2 (Даф-Мед). — 671 с. — ISBN 5-82270-035-5.

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