Iodosylbenzene Coordination Chemistry Relevant to Metal-Organic Framework Catalysis.

Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation-reduction processes and because the ligand-exchange chemistry intrinsic to the hypervalent center allows hypervalent iodine compounds to be applied to a broad array of oxidative substrate functionalization reactions. We recently developed methods to generate these compounds from O2 that are predicated on diverting reactive intermediates of aldehyde autoxidation toward the oxidation of aryl iodides. Coupling the aerobic oxidation of aryl iodides with catalysts that effect C-H bond oxidation would provide a strategy to achieve aerobic C-H oxidation chemistry. In this Forum Article, we discuss the aspects of hypervalent iodine chemistry and bonding that render this class of reagents attractive lynchpins for aerobic oxidation chemistry. We then discuss the oxidation processes relevant to the aerobic preparation of 2-(tert-butylsulfonyl)iodosylbenzene, which is a popular hypervalent iodine reagent for use with porous metal-organic framework (MOF)-based catalysts because it displays significantly enhanced solubility as compared with unsubstituted iodosylbenzene. We demonstrate that popular synthetic methods to this reagent often provide material that displays unpredictable disproportionation behavior due to the presence of trace impurities. We provide a revised synthetic route that avoids impurities common in the reported methods and provides access to material that displays predictable stability. Finally, we describe the coordination chemistry of hypervalent iodine compounds with metal clusters relevant to MOF chemistry and discuss the potential implications of this coordination chemistry to catalysis in MOF scaffolds.