Base‐Stabilized [PO]+/[PO2]+ Cations

The salts [(BAC)2PO][BF4] (5) and [(BAC)2PO2][BF4] (4) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO+ and PO2+ cations, respectively, coordinated to the singlet carbenes, have been prepared. Computational investigations reveal that the electronic structure of the PO+ cation is...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-12, Vol.58 (50), p.18276-18280
Main Authors: Zhou, Jiliang, Liu, Liu Leo, Cao, Levy L., Stephan, Douglas W.
Format: Article
Language:English
Subjects:
ambiphlicity
Carbenes
Cations
Computer applications
Coordination compounds
cyclopropenylidene
Electronic structure
Fluorides
PO+ cation
PO+ transfer
PO2+ cation
Potassium chloride
Salts
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Summary:The salts [(BAC)2PO][BF4] (5) and [(BAC)2PO2][BF4] (4) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO+ and PO2+ cations, respectively, coordinated to the singlet carbenes, have been prepared. Computational investigations reveal that the electronic structure of the PO+ cation is a hybrid between the charge‐localized and charge‐delocalized resonance forms, resulting in ambiphilic reactivity. Compound 5 reacts as a donor with the transition‐metal complex K2PtCl4 to furnish [[(BAC)2PO]2PtCl2][BF4]2 (6) and KCl. Remarkably, both 5 and 4 have shown to act as electrophiles undergoing reactions with fluoride anion, leading to [OPF2]− and (BAC)PO2F, respectively. PO+ and PO2+ cations stabilized by cyclopropenylidene have been prepared by an atomically precise delivery of P+ and O atoms. The former species exhibits ambiphilic reactivity, while both species acts as electrophiles in reactions with fluoride.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201912009