Premium
Base‐Stabilized [PO] + /[PO 2 ] + Cations
Author(s) -
Zhou Jiliang,
Liu Liu Leo,
Cao Levy L.,
Stephan Douglas W.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912009
Subject(s) - chemistry , delocalized electron , electrophile , reactivity (psychology) , singlet state , resonance (particle physics) , metal , fluoride , ion , crystallography , stereochemistry , medicinal chemistry , inorganic chemistry , excited state , organic chemistry , physics , medicine , alternative medicine , pathology , catalysis , particle physics , nuclear physics
Abstract The salts [(BAC) 2 PO][BF 4 ] ( 5 ) and [(BAC) 2 PO 2 ][BF 4 ] ( 4 ) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO + and PO 2 + 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 K 2 PtCl 4 to furnish [[(BAC) 2 PO] 2 PtCl 2 ][BF 4 ] 2 ( 6 ) and KCl. Remarkably, both 5 and 4 have shown to act as electrophiles undergoing reactions with fluoride anion, leading to [OPF 2 ] − and (BAC)PO 2 F, respectively.