Intramolekulare Reaktionen transienter Phosphenium‐ und Arsenium‐Ionen führen zur Bildung isolierbarer 9‐Phospha‐ und 9‐Arsena‐Fluorenium‐Ionen

Olaru, Marian; Duvinage, Daniel; Naß, Yannik; Malaspina, Lorraine A.; Mebs, Stefan; Beckmann, Jens

doi:10.1002/ange.202006728

Cited by 5 publications

(1 citation statement)

References 30 publications

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“…In our efforts to prepare kinetically stabilized, two‐coordinate and donor‐free pnictogenium ions we first directed our attention to bis( m ‐terphenyl)‐substituted species, [2,6‐Mes 2 C 6 H 3 ) 2 E] + ( 1 , E=P; 2 , E=As; [73] 3 , E=Sb; 4 , E=Bi; [74] Scheme 1) and [2,6‐Pmp 2 C 6 H 3 ) 2 E] + (E=P, As) [75] . The lighter homologues 1 and 2 turned out to be only transient species that quickly rearranged into the protonated 9‐phospha‐ and 9‐arsena‐fluorenes having the same elemental composition, whereas the heavier homologues 3 and 4 could be isolated and fully characterized (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Kinetically Stabilized Diarylpnictogenium Ions

2023

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The newly prepared and fully characterized stibenium and bismuthenium ions [RindMesE]+ (E=Sb, Bi; Rind=dispiro[fluorene‐9,3′‐(1′,1′,7′,7′‐tetramethyl‐s‐hydrindacen‐4′‐yl)‐5′,9′′‐fluorene) were rigorously compared to the previously communicated phosphenium and arsenium ions (E=P, As) as well as the bis(m‐terphenyl) pnictogenium ions [(2,6‐Mes2C6H3)2E]+ (E=Sb, Bi). It is demonstrated that the choice of the aryl substituents dramatically effects the molecular structures (e. g. the primary E−C bond lengths) and the electronic structures (e. g. the energy of the LUMOs).

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Section: Introductionmentioning

confidence: 99%

Kinetically Stabilized Diarylpnictogenium Ions

2023

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Kationische Carben‐Analoga: Donorfreie Phosphenium‐ und Arsenium‐Ionen

2021

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Chemiker waren schon immer begeistert von Carbenen und ihren Homologen, von ihrer faszinierenden Reaktivität und ihrem ambiphilen Charakter, der aus der besonderen elektronischen Struktur herrührt. Phosphenium‐ und Arsenium‐Ionen sind extrem reaktive kationische Spezies, deren Stabilisierung in kondensierter Phase bislang nur dadurch erreicht werden könnte, indem die positive Ladung durch elektromere Konjugation über mindestens einen elektronenreichen Substituenten (häufig eine Amidogruppe) delokalisiert wurde. Obwohl sie in der Gasphase beobachtet wurden, entzogen sich dikoordinierte Phosphenium‐ und Arsenium‐Ionen ohne stabilisierende Liganden für viele Jahrzehnte ihrer Isolierung. Hier zeigen wir, dass durch die geeignete Wahl aromatischer Substituenten dikoordinierte, donorfreie, Lewis supersaure Phosphenium‐ und Arsenium‐Ionen kinetisch stabilisiert werden können. Diese zeichnen sich durch einen elektronischen Singulett‐Grundzustand aus und weisen ein nicht‐besetztes p‐Orbital sowie ein freies Elektronenpaar mit dominierendem s‐Charakter auf.

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Cationic Carbene Analogues: Donor‐Free Phosphenium and Arsenium Ions

2021

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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.

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Intramolekulare Reaktionen transienter Phosphenium‐ und Arsenium‐Ionen führen zur Bildung isolierbarer 9‐Phospha‐ und 9‐Arsena‐Fluorenium‐Ionen

Cited by 5 publications

References 30 publications

Kinetically Stabilized Diarylpnictogenium Ions

Kinetically Stabilized Diarylpnictogenium Ions

Kationische Carben‐Analoga: Donorfreie Phosphenium‐ und Arsenium‐Ionen

Cationic Carbene Analogues: Donor‐Free Phosphenium and Arsenium Ions

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