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Access to Air‐Stable 1,3‐Diphosphacyclobutane‐2,4‐diyls by an Arylation Reaction with Arynes
Author(s) -
Ueta Yasuhiro,
Mikami Koichi,
Ito Shigekazu
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201601907
Subject(s) - aryne , aryl , steric effects , fluoride , chemistry , singlet state , substituent , medicinal chemistry , combinatorial chemistry , photochemistry , organic chemistry , inorganic chemistry , atomic physics , physics , alkyl , excited state
Tuning of the physicochemical properties of the 1,3‐diphosphacyclobutane‐2,4‐diyl unit is attractive in view of materials applications. The use of arynes is shown to be effective for installing relatively electron rich aryl substituents into the open‐shell singlet P‐heterocyclic system. Treatment of the sterically encumbered 1,3‐diphosphacyclobuten‐4‐yl anion with ortho ‐silylated aryl triflates in the presence of fluoride under appropriate conditions afforded the corresponding 1‐aryl 1,3‐diphosphacyclobutane‐2,4‐diyls. The air‐stable open‐shell singlet P‐heterocycles exhibit considerable electron‐donating character, and the aromatic substituent influences the open‐shell character, which is thought to be related to the property of p‐type semiconductivity. The P‐arylated 1,3‐diphosphacyclobutane‐2,4‐diyl systems can be further utilized as detectors of hydrogen fluoride (HF), which causes a remarkable change in their photoabsorption properties.