Auf zu neuen Ufern: Die stufenweise Hydrolyse eines Diphosphor‐Trikations ist eine effiziente Methode, ein ungewöhnliches ligandenstabilisiertes Dikation mit einem neuartigen kationischen [P4O4]2+‐Gerüst herzustellen (siehe Schema, grau C, Blau N, rot O, orange P). Diese Reaktion unterstreicht das Potenzial des Diphosphor‐Trikations als Quelle für Phosphor‐Bausteine, mit denen neuartige kationische Ring‐ und Clustersysteme aufgebaut werden können.
A door to new opportunities: The stepwise hydrolysis of a diphosphorus trication is an efficient method for the preparation of an unusual ligand‐stabilized dication that contains a novel cationic [P4O4]2+ framework (see Scheme; gray C, blue N, red O, orange P). This approach demonstrates the potential of the diphosphorus trication as a source for phosphorus building blocks to be used in the construction of novel cationic ring and cluster systems.
The trication (pyr3P2)3+ (1+, pyr = 3,5‐dimethylpyrazolyl) is used as a convenient pyrazolyl‐transfer reagent to convert 2‐pyridones, 4‐pyridones, and urea derivatives to pyrazolyl‐substituted pyridinium or guanidinium triflate salts. This conversion represents a new, efficient, and highly functional‐group‐compatible approach that yields the desired products conveniently and in high yields. Typically, this reaction proceeds by exchange of the carbonyl oxygen atom of the substrate for a pyrazolyl moiety. However, for the structurally related 3‐hydroxypyridines, a different reaction pathway occurs to give tripyridyl phosphites. The outcome of the reaction can be explained by the lactam–lactim tautomerism of the substrate and is discussed in detail. All reaction products were fully characterized by elemental analysis and multinuclear NMR, IR, and Raman spectroscopy, and the structural arrangements of most of the products were confirmed by X‐ray crystallography analysis.
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