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Free keywords:
REDUCTIVE ELIMINATION; DENSITY FUNCTIONALS; CRYSTAL-STRUCTURES; PD(III) COMPLEXES; BOND FORMATION; DINUCLEAR; CHEMISTRY; MECHANISM; ACTIVATION
Abstract:
Cooperative metal-metal (M-M) redox chemistry has the potential to lower activation barriers for redox transformations relevant to catalysis. Pd-2(III,III) complexes, generated by oxidation of Pd-2(II,II) complexes, have recently been implicated as intermediates in a variety of Pd-catalyzed C-H oxidation reactions. M-M redox synergy, mediated by Pd-Pd bond formation and cleavage, has been proposed to facilitate both oxidation and reductive elimination steps during various Pd-catalyzed directed C-H oxidation reactions. Herein, we report a transition state mimic for the oxidation of Pd-2(II,II) complexes which suggests that M-M redox synergy is involved in the oxidation of Pd-2(II,II) complexes to Pd-2(III,III) complexes.
