Spectroscopic Identification of the Dinitrogen Fixation and Activation by Metal Carbide Cluster Anions PtCn– (n = 4–6),Inorganic Chemistry

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Spectroscopic Identification of the Dinitrogen Fixation and Activation by Metal Carbide Cluster Anions PtCn– (n = 4–6)
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-12-27 , DOI: 10.1021/acs.inorgchem.2c03150
Shihu Du _{1,

2} , Xuegang Liu ₁ , Bangmin Ju ₁ , Jumei Zhang ₃ , Jinghan Zou ₁ , Gang Li ₁ , Hongjun Fan ₁ , Hua Xie ₁ , Ling Jiang ₁

Affiliation

Nitrogen fixation is confronted with great challenges in the field of chemistry. Herein, we report that single metal carbides PtC_n^– and PtC_nN₂^– (n = 4–6) are indispensable intermediates in the process of nitrogen fixation by mass spectrometry coupled with anionic photoelectron spectroscopy, quantum chemical calculations, and simulated density-of-state spectra. The most stable isomers of these cluster anions are characterized to have linear chain structures. The fixation and activation of dinitrogen are facilitated by the charge transfer from Pt and C_n to N₂. The significance of π back-donation of the 5d orbital of the Pt atom to the antibonding π orbits of N₂ for dinitrogen fixation and activation is discussed in detail. This study not only provides a theoretical basis at the molecular level for the activation of dinitrogen by mononuclear metal carbide clusters but also provides a new paradigm for dinitrogen fixation.

中文翻译：

金属碳化物簇阴离子 PtCn– (n = 4–6) 对二氮固定和活化的光谱鉴定

固氮在化学领域面临着巨大的挑战。在此，我们报告了单一金属碳化物 PtC _n^–和 PtC _n N ₂^– ( n = 4–6) 是固氮过程中不可或缺的中间体，通过质谱结合阴离子光电子能谱、量子化学计算和模拟密度-状态光谱。这些簇阴离子最稳定的异构体的特征是具有线性链结构。_{从 Pt 和 C n}到 N ₂的电荷转移促进了二氮的固定和活化. 详细讨论了 Pt 原子的 5d 轨道 π 回馈 N ₂的反键合 π 轨道对于双氮固定和活化的意义。该研究不仅为单核金属碳化物团簇活化二氮提供了分子水平的理论基础，也为二氮固定提供了新的范式。

更新日期：2022-12-27

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