Title:
Phospholenes from Phosphabenzenes by Selective Ring Contraction
Author(s):
Lin, Jinxiong; Coles, Nathan T.; Dettling, Lea; Steiner, Luca; Witte, Jan Felix; Paulus, Beate; Müller, Christian
Year of publication:
2022
Available Date:
2023-01-02T11:20:14Z
Abstract:
A 3-aminofunctionalized phosphabenzene (phosphinine) was 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 labelling experiments and quantum chemical calculations, a rational mechanism for this hitherto unknown conversion is proposed.
Part of Identifier:
e-ISSN (online): 1521-3765
Keywords:
DFT calculations
phosphorus heterocycles
phospholene
Phosphinic acid
X-Ray Crystallography
DDC-Classification:
540 Chemie und zugeordnete Wissenschaften
Publication Type:
Wissenschaftlicher Artikel
URL of the Original Publication:
DOI of the Original Publication:
Journaltitle:
Chemistry—A European Journal
Department/institution:
Biologie, Chemie, Pharmazie
Institut für Chemie und Biochemie
Comments:
Die Publikation wurde aus Open Access Publikationsgeldern der Freien Universität Berlin gefördert.