Stable acyclic arsenium cations R 2 As + ,isoelectronic analogues of germylenes,a re rare in comparison to the corresponding phosphenium cations.T he first example of ad iphosphaarsenium salt, [{(Dipp) 2 P} 2 As][Al{OC-(CF 3 ) 3 } 4 ]·1 1 = 2 PhMe,isdescribed. This salt exhibits remarkable stability due to the delocalisation of alone pair from aplanar phosphorus centre into the vacant p-orbital at arsenic;t he bonding in 2 has been probed by DFT calculations.Anattempt to synthesise an analogous diphosphaphosphenium salt unexpectedly generated the cyclic phosphonium salt [cyclo-{(Mes)P} 2 P(Mes) 2 ][BAr F 4 ]·CyMe through the cyclisation of ap utative phosphine-substituted diphosphene cation intermediate.