钴配合物催化氮气活化转化的研究进展

doi:10.6023/cjoc202602020

摘要/Abstract

实现温和条件下氮气的活化转化具有重要意义。由于氮气分子的高键能和非极性的特点,其反应活性较低。过渡金属配合物为氮气的活化转化提供了一种有效策略。目前,过渡金属促进的氮气活化转化研究主要集中在前过渡金属体系。由于前过渡金属与氮原子结合能力相对较强,不利于催化转化的发生,而后过渡金属在实现氮气活化与含氮产物释放的平衡方面具有一定的优势。本文系统总结了后过渡金属钴配合物在催化氮气活化转化方面的研究进展,主要包括简单钴配合物、钳型配体钴配合物、氮杂环卡宾钴配合物、双齿膦配体钴配合物以及双/多核钴配合物等催化体系,依据催化剂核数的不同（单核或双(多)核）以及氮气活化后产物的不同（三(三甲基硅基)胺或氨气）对催化反应进行了归纳和总结,并对相应的反应机理进行了探讨。

关键词: 钴配合物, 催化, 氮气活化转化, 反应机制

The achievement of the activation and functionalization of dinitrogen under mild conditions is of great significance. Owing to its high bond dissociation energy and non-polar nature, the dinitrogen molecule exhibits very low reactivity. Transition metal complexes provide an effective strategy for the activation and functionalization of dinitrogen. At present, the research on nitrogen activation and functionalization promoted by transition metals mainly focuses on the early transition metal systems. The relatively strong bonding between early transition metal and nitrogen atom limits their potential for catalytic turnover. However, late transition metals have certain advantages in achieving a balance between nitrogen activation and the release of nitrogen-containing products. This article systematically reviews recent progress in the catalytic activation and functionalization of dinitrogen by late transition cobalt complexes, including catalytic systems such as simple cobalt complexes, pincer-ligated cobalt complexes, N-heterocyclic carbene (NHC)-ligated cobalt complexes, bidentate phosphine-ligated cobalt complexes, and bi-/polynuclear cobalt complexes. The catalytic reactions are categorized based on the nuclearity of the cobalt catalysts (mononuclear or binuclear/polynuclear) and the nature of the nitrogen-derived products (tris(trimethylsilyl)amine (N(SiMe₃)₃) or ammonia). Corresponding reaction mechanisms are also discussed. In summary, cobalt complexes have gradually attracted widespread attention in the field of catalytic nitrogen activation and functionalization, exhibiting promising reactivity (A pincer PCP-cobalt complex affords a TON of up to 351(42) for N₂-to-N(SiMe₃)₃ conversion). However, the reaction modes of existing catalytic systems remain relatively limited, with N(SiMe₃)₃ being the predominant product upon nitrogen activation. Furthermore, all current systems rely on strong alkali metal reductants or strong Brønsted acids as proton sources, leading to poor overall reaction compatibility.

Key words: cobalt complex, catalysis, dinitrogen activation and functionalization, reaction mechanism

引用此文

程振东, 高亚飞. 钴配合物催化氮气活化转化的研究进展[J]. 有机化学, doi: 10.6023/cjoc202602020.

Cheng Zhendong, Gao Yafei. Research Progress on Catalytic Dinitrogen Activation and Functionalization Mediated by Cobalt Complexes[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202602020.

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