Unusual, if not unprecedented, effects of transition-metal ions and ligands are discovered when simple metal oxides or carbides activate methane in the gas phase in manners reminiscent of oriented external electric fields.
In the course of combined computational and mass spectrometry-based mechanistic studies, recently we came across rather unusual, if not unprecedented, effects of transition-metal ions and ligands when simple metal oxides or carbides are subjected to thermal gas-phase reactions with methane. Interestingly, “Gedankenexperiments” demonstrate how these effects can be modeled using oriented external electric fields (OEEFs), thus expanding their predicted role as “smart reagents” (Shaik et al., Nat. Chem., 2016, 8, 1091), and further suggesting that the OEEFs may be used in controlling the adsorption/desorption behavior of methane as well as serving as a tool to explore mechanistic features.