PHOSPHORANEDIYL-1,3,5-TRIPHOSPHINANES PHO SPHONIO-1,3,5-TRIPHOSPHININE CATIONS/

Depending on the reaction conditions, the condensation of triphenylpho sphonium bis(trimethylsilyl)methylide 1 with phosphorus trichloride an d phosphorus tribromide gives the cyclic trimers (Ph(3)P=CP-X)(3), X = Cl, Br, is(triphenylphosphoranediyl)-1,3,5-triphosphinanes 3 and 5. I n solution the compounds dissociate to give the ionic forms 4 and 6 wh ich rapidly exchange the halide between the halophosphine and the phos phenium moieties. The exchange is slowed down when the halide ion is r eplaced by a tosylate ion. Substitution of the covalent chloride of 4 for diphenylphosphino groups gives again an ionic product 10, while th e introduction of a morpholino group as well as the replacement of all chloride by triflate give dicationic compounds 12 and 13. Reaction of 3 with gallium trichloride finally leads to the tris(triphenylphospho nio)-1,3,5-triphosphinine trication as a major equilibrium participant .