The mechanism of Pd-catalyzed aromatic C–H oxidation chemistry continues to be vigorously discussed. Historically, Pd(II)/Pd(IV) catalysis cycles have been proposed. Herein, we present a detailed study of Pd(OAc)2-catalyzed aromatic C–H chlorination and propose dinuclear Pd(III) complexes as intermediates. We have identified a succinate-bridged dinuclear Pd(II) complex, which self-assembles during catalysis, as the catalyst resting state. In situ monitoring of catalysis has revealed that chlorination proceeds with turnover-limiting oxidation of a dinuclear resting state, and that acetate ions, liberated during the formation of the catalyst resting state, catalyze the bimetallic oxidation. Informed by reaction kinetics analysis, relevant dinuclear Pd(III) complexes have been prepared and observed to undergo selective C–Cl reductive elimination. Based on the combination of kinetic data obtained during catalysis and explicit structural information of relevant intermediates, we propose a Pd(II)2/Pd(III)2 catalysis cycle for Pd(OAc)2-catalyzed aromatic C–H chlorination.
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