Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. X. Zur Solvolyse von Phosphor(III/V)-oxiden

Contributions to the Chemistry of Phosphorus Compounds with Adamantane Structure. X. Solvolysis of Phosphorus(III/V) Oxides The phosphorus(III/V) oxides of adamantan-like structure have been prepared by oxydation of phosphorus or of phosphorus trioxide with oxygen and characterized by analysis in water solution and by ³¹P n.m.r. spectroscopy. Paper chromatographic and n.m.r. studies show that the alcoholysis of the phosphorus(III/V) oxides leads to tri-, di-, and monoesters of phosphorous acid and also to mono-, di-, and cyclotriphosphoric acid, in dependence on their P^III and P^V contents. Nucleophilic attack by the alcohol takes place not statistically but in principle on the P^III atoms of the phosphorus(III/V) oxide molecule and their primary degradation products. In analogy to the alcoholysis the hydrolysis of the phosphorus(III/V) oxides yields phosphorous acid, mono-, di-, and cyclotriphosphoric acid. The mechanism of degradation is discussed.