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- W2016008074 abstract "Phosphoniumhydrogendihalogenide [R3PR′] [XHY] (X = Y = Cl, Br, I; X = Br, Y = Cl) bzw. [R3PH] HBr2 erhält man als extrem hydrolyseempfindliche Kristalle durch Umsetzung von Phosphoniumhalogeniden bzw. tertiären Phosphanen mit Halogenwasserstoff. IR-spektroskopischen Befunden zufolge enhalten die Anionen [XHX]− in den festen Hydrogendihalogeniden zumeist symmetrische Wasserstoffbrücken. Aus der Protonenresonanz der Anionen wird geschlossen, daß in den Lösungen der Substanzen eine geringe (X = Cl, Br) oder auch stäkere (X = I) Dissoziation nach HX2− ⇌ X− + HX erfolgt. Beim Erwärmen spalten die Feststoffe Halogenwasserstoff unter Bildung von [R3PR′] X bzw. [R3PH]X ab. Die Hydrogenbromidchloride [R3PR′] [BrHCl] eliminieren hierbei ausschileßlich HCl. NMR-Untersuchungen (1H und 31P) an Lösungen von [R3PH] HBr2 (R = Ph, 1-Naphthyl) sowie von HBr und Ph3P in CDCl3 mit variierendem Molverhältinis beider Komponenten zeigen, daß hier ein schneller Austausch des Protons zwischen den konkurrierenden Lewisbasen R3P und Br− stattfindet. Phosphonium Salts with Hydrogen Dihalide Anions HCl2−, HBr2−, HI2−, or HBrCl− Phosphonium hydrogen dihalides [R3PR′][XHY] (X = Y = Cl, Br, I; X = Br, Y = Cl) resp. [R3PH]HBr2 are obtained as extremely hydrolyzable crystals by reaction of phosphonium halides or tertiary phosphanes with hydrogen halide. According to IR spectroscopic results the solid compounds mostly contain anions [XHX]− with symmetric hydrogen bonds. In solution 1H NMR measurements show a slight (X = Cl, Br) or considerable (X = I) dissociation according to HX2− ⇌ X− + HX. On heating the solid compounds decompose with formation of hydrogen halide and [R3PR′]X or [R3PH]X. In this process the hydrogen bromidechlorides [R3PR′][BrHCl] exclusively eliminate HCl. NMR studies (1H und 31P) with solutions containing [R3PH]HBr2 (R = phenyl, 1-naphtyl) or HBr and Ph3P in varying molar ratios show that a fast proton exchange between the competing Lewis bases R3P and Br− exists." @default.
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- W2016008074 title "Phosphoniumsalze mit Hydrogendihalogenidanionen HCl2?, HBr2? Hl2? oder HBrCl?" @default.
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- W2016008074 doi "https://doi.org/10.1002/zaac.19875510820" @default.
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