Methane Activation by Closed-Shell Tantalum Sulfide Anions TaS3-
Methane is a vital feedstock while the in-trinsic inertness of CH4 molecule hinders the conversion of methane under mild con-ditions.Investigating and understanding the mechanism of methane activation is of great importance in chemistry.In this study,tantalum sulfide anions TaS3-were generated by laser ablation method and mass-selected by a quadrupole mass filter to react with methane,ethane,and propane in an ion funnel trap reactor under thermal collision conditions.The reactant and product ions were detected by a time-of-flight mass spectrometer.Experimental results demonstrate that TaS3-is able to adsorb all of the alkane molecules and break the robust C-H bonds.Further density functional theory calculations reveal that TaS3-is a closed-shell species and effectively activates methane via the Taδ+-Sδ-Lewis acid-base pair(LABP,CH4+Taδ+-Sδ-→CH3-Ta-S-H).With a comparative study with NbS3-that contains the Nbδ+-Sδ-LABP,the higher reactivity of TaS3-than that of NbS3-can be attributed to the more acidity of Taδ+than that of Nbδ+.To the best of our knowledge,this study reports the first example of gas phase species TaS3-to activate methane through the metal-sulfur LABP under thermal collision conditions.
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