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

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