Analytically pure chloride and bromide salts of two different cyclic triphosphenium cations are prepared by the reaction of PX3 (X=Cl, Br) in the presence of the halogen-scavenging reagent cyclohexene. For the brominated species, the neutral, volatile 1,2-dibromocyclohexane byproduct is readily removed under reduced pressure, and the desired salts are obtained in high yield. Reactions involving phosphorus trichloride are complicated by the formation of salts containing both chloride and hydrogen dichloride anions. Reactivity experiments on potential undesired halogenated diphosphine byproducts suggest that the formation of such species can be prevented by increasing the concentration of cyclohexene employed in the reaction.
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