Base‐Stabilized [PO] + /[PO 2 ] + Cations

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.