Efficient Room‐Temperature Activation of Methane by TaN+ under C−N Coupling

The thermal reaction of diatomic tantalum nitride cation [TaN]+ with methane has been explored using FT‐ICR mass spectrometry complemented by high‐level quantum chemical calculation; based on this combined experimental/computational approach, mechanistic aspects of this novel, highly efficient C−N coupling process have been uncovered. In distinct contrast to [TaN]+, its lighter congeners [VN]+ and [NbN]+ are inert towards methane under ambient conditions, and the origins of the remarkably variable efficiencies of the three metal nitrides are uncovered by CCSD(T) calculations.MeTa‐lated: Thermal activation of methane by [TaN]+ under C−N coupling and formation of H2 was detected by mass spectrometry and confirmed by quantum chemical calculations. The lighter congeners [VN]+ and [NbN]+ are inert towards methane under the same conditions. (In the picture the signal labeled with “×” arises from reactions with background contaminants.)Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137504/1/anie201606259-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137504/2/anie201606259.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137504/3/anie201606259_am.pd