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Metal-iodosylarene complexes have been recently viewed as a second oxidant alongside of the well-known high-valent metal-oxo species. Extensive efforts have been exerted to unveil the structure-function relationship of various metal-iodosylarene complexes. In the present manuscript, density functional theoretical calculations were employed to investigate such relationship of a specific manganese-iodosylbenzene complex [Mn III (TBDAP)(PhIO)(OH)] 2+  ( 1 ). Our results fit the experimental observations and revealed new mechanistic findings.  1  acts as a stepwise 1e+1e oxidant in sulfoxidation reactions. Surprisingly, C-H bond activation of 9,10-dihydroanthracene (DHA) by  1  proceeds via a novel ionic hydride transfer/proton transfer (HT/PT) mechanism. As a comparison to  1 , the electrophilicity of an iodosylbenzene monomer PhIO was investigated. PhIO performs concerted 2e-oxidations both in sulfoxidation and C-H activation. Hydroxylation of DHA by PhIO was found to proceed via a novel ionic and concerted proton-transfer/hydroxyl-rebound mechanism involving 2e-oxidation to form a transient carbonium species.

Theoretical Study on the Structural-Function Relationship of Manganese(III)-Iodosylarene Adducts