We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr)][OTf] (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr)][OTf] gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.

Oxidation of heavy triphenyl pnictines with Weiss’ reagent ([PhI(Pyr)2]2+) gives dicationic Pn(v) coordination complexes in a single step.

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 <br>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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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 <br>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.