The Reagent Diphenyldiselane/Iodine: No Phenylselenenyl Iodide but a Charge Transfer Complex with Cyclic Moieties

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Abstract
Eight‐membered, slightly puckered rings [Se(Ph)Se(Ph)IISe(Ph)Se(Ph)II] are present in the crystalline title compound 3c; in analogy to the bulky subsituted species 2a, b, the structure PhSeI had been expected. 3c, with its hypervalent iodine and selenium atoms, acts as “frozen‐in intermediate” of the dismutation of seleniumselenium bonds with iodine. The rapidly established equilibria between the reactants 1 and the products 2 and 3 provide an explanation for the iodine‐catalyzed crystallization of rigid selenium melts. equation image