Reactions of PhIX2 I(III) Oxidants with Heavy Triphenyl Pnictines

The reactions of [PhI(pyridine)2]2+, PhI(OAc)2 and PhI(OTf)(OAc) with Ph3As, Ph3Sb and Ph3Bi are described. The reactions of [PhI(pyridine)2]2+ with Ph3Sb and Ph3Bi affords dicationic Pn(V) complexes ligated by pyridine in one step. These were previously reported by Burford in multi step syntheses. Reactions with PhI(OAc)2, which were already known for Sb and Bi giving Pn(V) diacetates, was confirmed to give the same type of compound for As. Reactions with
PhI(OAc)(OTf) were less clean, resulting in the isolation of iodonium cations [Ph-I-Ph]+ for As and Bi, while Ph3Sb gave an oxobridged di-antimony species characteristic of the decomposition of a high valent triflate bound species.

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