Electronic Effects on Room-Temperature, Gas-Phase C-H Bond Activations by Cluster Oxides and Metal Carbides: The...

This Perspective discusses a story of one molecule (methane), a few metal-oxide cationic clusters (MOCCs), dopants, metal-carbide cations, oriented-electric fields (OEFs), and a dizzying mechanistic landscape of methane activation! One mechanism is hydrogen atom transfer (HAT), which occurs whenever the MOCC possesses a localized oxyl radical (M-O^•). Whenever the radical is delocalized, e.g., in [MgO]_n^•+ the HAT barrier increases due to the penalty of radical localization. Adding a dopant (Ga₂O₃) to [MgO]₂^•+ localizes the radical and HAT transpires. Whenever the radical is located on the metal centers as in [Al₂O₂]^•+ the mechanism crosses over to proton-coupled electron transfer (PCET), wherein the positive Al center acts as a Lewis acid that coordinates the methane molecule, while one of the bridging oxygen atoms abstracts a proton, and the negatively charged CH₃ moiety relocates to the metal fragment. We provide a diagnostic plot of barriers vs reactants' distortion energies, which allows the chemist to distinguish HAT from PCET. Thus, doping of [MgO]₂^•+ by Al₂O₃ enables HAT and PCET to compete. Similarly, [ZnO]^•+ activates methane by PCET generating many products. Adding a CH₃CN ligand to form [(CH₃CN)ZnO]^•+ leads to a single HAT product. The CH₃CN dipole acts as an OEF that switches off PCET. [MC]⁺ cations (M = Au, Cu) act by different mechanisms, dictated by the M⁺-C bond covalence. For example, Cu⁺, which bonds the carbon atom mostly electrostatically, performs coupling of C to methane to yield ethylene, in a single almost barrier-free step, with an unprecedented atomic choreography catalyzed by the OEF of Cu⁺.