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Updated: Aug 21, 2025

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Phospholenes from Phosphabenzenes by Selective Ring Contraction
Jinxiong Lin1, Nathan T Coles1,2, Lea Dettling1
1Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34/36, 14195, Berlin, Germany.
Abstract:
A 3-amino-functionalized phosphabenzene (phosphinine) has been synthesized and structurally characterized. The pyramidalized nitrogen atom of the dimethylamino substituent indicates only a weak interaction between the lone pair of the nitrogen atom and the aromatic phosphorus heterocycle, resulting in somewhat basic character. It turned out that the amino group can indeed be protonated by HCl. In contrast to pyridines, however, the phosphabenzene-ammonium salt undergoes a selective ring contraction to form a hydroxylphospholene oxide in the presence of additional water. Based on deuterium labeling experiments and quantum chemical calculations, a rational mechanism for this hitherto unknown conversion is proposed.
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