Oxidative Addition of Nitro-Perylenediimide onto Palladium(0): A Theoretical and Experimental Study

Abstract

Palladium-catalyzed cross-coupling reactions, particularly the Suzuki–Miyaura coupling, are efficient tools for constructing C–C bonds due to their exceptional versatility and efficiency. Recently, nitroarenes have been explored as new electrophilic substrates in palladium-catalyzed denitrative Suzuki–Miyaura coupling, offering an alternative to traditionally used organic halides or triflates. The oxidative addition of nitro derivatives onto palladium catalysts remains challenging and often requires harsh conditions and expensive catalytic systems. Nevertheless, we recently demonstrated that nitro-perylenediimide derivatives can effectively engage in various cross-couplings with unsophisticated Pd(PPh₃)₄ as a catalytic system. The mechanistic study of the oxidative addition step for this particular class of nitro derivatives revealed an unprecedented single electron transfer event, which is supported by a comprehensive range of analyses including NMR, X-ray diffraction, HRMS and EPR experiments, complemented with cyclic voltammetry, and theoretical calculations.