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Updated: Jul 6, 2025
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Manipulating Reactivity of Ir(CH2)0-2+ Cations toward Dinitrogen at Room Temperature: A Unique Dependence on the
Yong-Qi Ding1,2, Feng-Xiang Zhang1, Ying Li1
1Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
Abstract:
Nitrogen (N2) activation at room temperature has long been a great challenge. Therefore, the rational design of reactive species to adsorb N2, which is a prerequisite for cleavage of the strong N≡N triple bond in industrial and biological processes, is highly desirable and meaningful. Herein, the N2 adsorption process is controlled by regulating the types and numbers of organic ligands, and the organic ligands are produced through the reactions of Ir+ with methane and ethane. CH4 molecules dissociate on the Ir+ cations to form Ir(CH2)1,2+. The reaction of Ir+ with C2H6 can generate HIrC2H3+, which is different from the structure of Ir(CH2)2+ obtained from Ir+/CH4. The reactivity order of N2 adsorption is Ir(CH2)2+ > HIrC2H3+ ≫ HIrCH+ ≈ Ir+ (almost inert under similar reaction conditions), indicating that different organic ligand structures affect reactivity dramatically. The main reason for this interesting reactivity difference is that the lowest unoccupied molecular orbital (LUMO) level of Ir(CH2)2+ is much closer to the highest occupied molecular orbital (HOMO) level of N2 than those of the other three systems. This study provides new insights into the adsorption of N2 on metal-organic ligand species, in which the organic ligand dominates the reactivity, and it discovers new clues in designing effective transition metal carbine species for N2 activation.
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