Iodine-Iodine Cooperation Enables Metal-Free C-N Bond-Forming Electrocatalysis via Isolable Iodanyl Radicals.

ABSTRACT: Small molecule redox mediators convey interfacial electron transfer events into bulk solution and can enable diverse substrate activation mechanisms in synthetic electrocatalysis. Here, we report that 1,2-diiodo-4,5-dimethoxybenzene is an efficient electrocatalyst for C-H/E-H coupling that operates at as low as 0.5 mol % catalyst loading. Spectroscopic, crystallographic, and computational results indicate a critical role for a three-electron I-I bonding interaction in stabilizing an iodanyl radical intermediate (i.e., formally I(II) species). As a result, the optimized catalyst operates at more than 100 mV lower potential than the related monoiodide catalyst 4-iodoanisole, which results in improved product yield, higher Faradaic efficiency, and expanded substrate scope. The isolated

SUBMITTER: Frey BL 

PROVIDER: S-EPMC10251780 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature