Spectroscopic Characterization of Thermal Methane Activation by Lewis‐Acid‐Base Pair in a Gas‐Phase Metal Nitride Anion Ta2N3−

Activation and transformation of methane is one of the "holy grails" in catalysis. Understanding the nature of active sites and mechanistic details via spectroscopic characterization of the reactive sites and key intermediates is of great challenge but crucial for the development of novel strategies for methane transformation. Herein, by employing photoelectron velocity-map imaging (PEVMI) spectroscopy in conjunction with quantum chemistry calculations, the Lewis acid-base pair (LABP) of [Taδ+ -Nδ- ] unit in Ta2 N3- acting as an active center to accomplish the heterolytic cleavage of C-H bond in CH4 has been confirmed by direct characterization of the reactant ion Ta2 N3- and the CH4 -adduct intermediate Ta2 N3 CH4- . Two active vibrational modes for the reactant (Ta2 N3- ) and four active vibrational modes for the intermediate (Ta2 N3 CH4- ) were observed from the vibrationally resolved PEVMI spectra, which unequivocally determined the structure of Ta2 N3- and Ta2 N3 CH4- . Upon heating, the LABP intermediate (Ta2 N3 CH4- ) containing the NH and Ta-CH3 unit can undergo the processes of C-N coupling and dehydrogenation to form the product with an adsorbed HCN molecule.