No abstract

Oxidation of a 1,4-di-iodobenzene having four adjacent p-tBu-C6H4 group (Ar′) substituents (1) yields the hypervalent iodine compound 1,4-[I(OAc)2]2-2,3,5,6-Ar′4-C6 (2), that undergoes cyclization to produce dicyclic di-iodonium salt (3).

Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electron lone pairs of electronegative atoms. This study examines the impact of remote substituents on select families of HVI compounds as means to achieve predictable two-dimensional extended solid-state materials. Crystallographic analyses of 10 HVI compounds from several related classes of λ3 organoiodine­(III) compounds, (diacetoxyiodo)­benzenes, (dibenzoatoiodo)­benzenes, [bis­(trifluoroacetoxy)­iodo]­benzenes, and μ-oxo-[(carboxylateiodo)­benzenes], provide insights into how remote substituents and the choice of carboxylate groups can impact intermolecular interactions in the solid state.

Iodonium ylides (ArI=CR(R")) represent unusual hypervalent iodine(III) sources of carbene equivalents. While their reactivity is well-described, their detailed structural chemistry is somewhat limited due to their thermal instability. Cyclic iodonium ylides typically have greater thermal stability than acyclic ylides, but so far few such materials have been examined by single crystal X-ray diffraction methods. This report details the synthesis of two cyclic iodonium ylides and their association in the solid state by intermolecular I•••O interactions.