Reactivity of Nickel Cations Liganded by Acetylacetone and Benzoylacetone with N 2 : Organic Ligand Effects

作者：Fengxiang Zhang, Yiheng Zhang, Min Kou, Yilan Li, Yuan Gao, Jun Zhu, Xianglei Kong, Jia‐Bi Ma · 发表于：The Journal of Physical Chemistry Letters · 年份：2025 · DOI：10.1021/acs.jpclett.5c01977 · 被引用次数：4 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Ammonia Synthesis and Nitrogen Reduction、Catalytic Processes in Materials Science

N 2 adsorption on metal sites under mild conditions and its dependence on the chemical environment are crucial for understanding the fundamental mechanism and designing an efficient catalyst. Here, electrospray ionization mass spectrometry (ESI-MS) experiments reveal distinct differences in N 2 binding capabilities among nickel complexes: both [(acetylacetonato)Ni] + and [(benzoylacetonato)Ni] + gas-phase cations exhibit high N 2 adsorption efficiency, while the bare Ni + and [(benzoylacetone)Ni(acetonitrile)] + cations show negligible reactivity toward N 2 . Density functional theory calculations reveal that organic ligands modulate the nickel oxidation state from +1 in the isolated Ni + to +2 in organometallic complexes, thereby enhancing the electrophilicity of the metal center and promoting N 2 chemisorption. The stabilization of N 2 adsorption products is further driven by (1) the formation of stable coordination bonds and (2) increased vibrational degrees of freedom, which facilitate thermal energy redistribution. In addition, steric hindrance from the acetonitrile ligand significantly suppresses the N 2 adsorption. Frontier orbital analysis confirms the σ-donation from the lone pairs of N 2 to unoccupied Ni- d orbitals. This work advances the understanding of the synergistic effects between organic ligands and transition metals in N 2 adsorption and activation.