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Cationic Carbene Analogues: Donor‐Free Phosphenium and Arsenium Ions
Author(s) -
Olaru Marian,
Mebs Stefan,
Beckmann Jens
Publication year - 2021
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.202107975
Subject(s) - cationic polymerization , lone pair , carbene , chemistry , substituent , reactivity (psychology) , ion , singlet state , photochemistry , lewis acids and bases , stereochemistry , polymer chemistry , molecule , organic chemistry , catalysis , excited state , atomic physics , physics , medicine , alternative medicine , pathology
Abstract Carbenes and their analogues have constantly enthralled chemists with their intriguing reactivity of ambiphilic character stemming from their electronic structures. Phosphenium and arsenium ions are fiercely reactive cationic species, the stabilization of which has been so far achieved in the condensed phase by dispersing the positive charge through electromeric conjugation with at least one electron‐rich substituent (frequently amido groups). Although observed in the gas phase, the isolation of dicoordinate phosphenium and arsenium ions lacking such stabilizing ligands has eluded chemists for decades. Herein we show that by judicious choice of aromatic substituents, dicoordinate, donor‐free, Lewis‐superacidic phosphenium and arsenium ions can be kinetically stabilized. They feature singlet electronic ground states possessing a vacant p‐orbital and an electron lone pair with predominantly s‐character.