Na-Promoted Bimetallic Hydroxide Nanoparticles for Aerobic C–H Activation: Catalyst Design Principles and Insights into Reaction Mechanism

A precious metal-free bimetallic Fe_<i>x</i>Mn_1-<i>x</i>(OH)_<i>y</i> hydroxide catalyst was developed that is capable of catalyzing aerobic C-H oxidation reactions at low temperatures, without the need for an initiator, relying sustainably on molecular oxygen. Through a systematic synthetic effort, we scanned a wide nanoparticle synthesis parameter space to lay out a detailed set of catalyst design principles unraveling how the Fe/Mn cation ratio, NaOH(aq) concentration used in the synthesis, catalyst washing procedures, extent of residual Na⁺ promoters on the catalyst surface, reaction temperature, and catalyst loading influence catalytic C-H activation performance as a function of the electronic, surface chemical, and crystal structure of Fe_<i>x</i>Mn_1-<i>x</i>(OH)_<i>y</i> bimetallic hydroxide nanostructures. Our comprehensive XRD, XPS, BET, ICP-MS, ¹H NMR, and XANES structural/product characterization results as well as mechanistic kinetic isotope effect (KIE) studies provided the following valuable insights into the molecular level origins of the catalytic performance of the bimetallic Fe_<i>x</i>Mn_1-<i>x</i>(OH)_<i>y</i> hydroxide nanostructures: (i) catalytic reactivity is due to the coexistence and synergistic operation of Fe³⁺ and Mn³⁺ cationic sites (with minor contributions from Fe²⁺ and Mn²⁺ sites) on the catalyst surface, where in the absence of one of these synergistic sites (i.e., in the presence of monometallic hydroxides), catalytic activity almost entirely vanishes, (ii) residual Na⁺ species on the catalyst surface act as efficient electronic promoters by increasing the electron density on the Fe³⁺ and Mn³⁺ cationic sites, which in turn, presumably enhance the electrophilic adsorption of organic reactants and strengthen the interaction between molecular oxygen and the catalyst surface, (iii) in the fluorene oxidation reaction the step dictating the reaction rate likely involved the breaking of a C-H bond (<i>k</i>_H<i>/k</i>_D = 2.4), (iv) reactivity patterns of a variety of alkylarene substrates indicate that the C-H bond cleavage follows a stepwise PT-ET (proton transfer-electron transfer) pathway.