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Depending on the reaction conditions, the condensation of triphenylphosphonium bis(trimethylsilyl)methylide 1 with phosphorus trichloride and phosphorus tribromide gives the cyclic trimers (Ph 3 P=CP-X) 3 , X = Cl, Br, trihalo-tris(triphenylphosphoranediyl)-1,3,5- triphosphinanes 3 and 5. In solution the compounds dissociate to give the ionic forms 4 and 6 which rapidly exchange the halide between the halophosphine and the phosphenium moieties. The exchange is slowed down when the halide ion is replaced by a tosylate ion. Substitution of the covalent chloride of 4 for diphenylphosphino groups gives again an ionic product 10, while the 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(triphenylphosphonio)-1,3,5-triphosphinine trication as a major equilibrium participant.

zeitschrift für naturforschung b

Phosphorandiyl-1,3,5-triphosphinane/ Phosphonio-1,3,5-triphosphinin Kationen/ Phosphoranediyl-1,3,5-triphosphinanes / Phosphonio-1,3,5-triphosphinine Cations