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. 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 review systematically outlines 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 turnover number (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, 2026, 46(7): 2604-2621.

Zhendong Cheng, Yafei Gao. Research Progress on Catalytic Dinitrogen Activation and Functionalization Mediated by Cobalt Complexes[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2604-2621.

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图/表 28

图1. 简单钴配合物催化氮气到三(三甲基硅基)胺的转化

Figure 1. Catalytic conversion of N2 into N(SiMe3)3 by simple cobalt complexes

图2. 联吡啶配体(bpy)存在下Co2(CO)8催化氮气分子转化为三(三甲基硅基)胺的可能途径

Figure 2. Possible route for the catalytic conversion of N2 into N(SiMe3)3 by Co2(CO)8 in the presence of bpy ligand

图3. PSiMeP钳形配体支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 3. Synthesis of cobalt-N2 complexes supported by PSiMeP pincer ligand and their application in catalyzing the conversion of N2 into N(SiMe3)3

图4. 含环己基卡宾配位的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 4. Synthesis of ICy coordinated cobalt-N2 complexes and their application in catalyzing the conversion of N2 into N(SiMe3)3

图5. NpNP支撑的钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 5. Synthesis of cobalt complexes supported by NpNP and their application in catalyzing the conversion of N2 into N(SiMe3)3

图6. NpNP支撑的钴配合物催化氮气分子转化为三(三甲基硅基)胺的可能途径

Figure 6. Possible route for the catalytic conversion of N2 into N(SiMe3)3 by cobalt complexes supported by NpNP

图7. QuiNacNacP支撑的钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 7. Synthesis of cobalt complexes supported by QuiNacNacP and their application in catalyzing the conversion of N2 into N(SiMe3)3

图8. PSiHP钳形配体支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 8. Synthesis of a cobalt-N2 complex supported by PSiHP pincer ligand and its application in catalyzing the conversion of N2 into N(SiMe3)3

图9. PSiHP钳形配体支撑的钴氮气配合物催化氮气分子转化为三(三甲基硅基)胺的可能途径

Figure 9. Possible route for the catalytic conversion of N2 into N(SiMe3)3 by cobalt-N2 complex supported by PSiHP pincer ligand

图10. 含1,2-双(二环己基膦基)-乙烷配位的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 10. Synthesis of dcpe coordinated cobalt-N2 complexes and their application in catalyzing the conversion of N2 into N(SiMe3)3

图11. PCP钳形配体支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 11. Synthesis of cobalt-N2 complexes supported by PCP pincer ligand and their application in catalyzing the conversion of N2 into N(SiMe3)3

图12. PNN钳形配体支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 12. Synthesis of a cobalt-N2 complex supported by PNN pincer ligand and its application in catalyzing the conversion of N2 into N(SiMe3)3

图13. 硅宾对PSiMeP钳形钴配合物催化氮气分子转化为三(三甲基硅基)胺的影响

Figure 13. Effect of a silylene ligand on the catalytic conversion of N2 into N(SiMe3)3 by cobalt-N2 complexes supported by PSiMeP pincer ligand

图14. 双硅宾钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 14. Synthesis of bis(silylene) cobalt complexes and their application in catalyzing the conversion of N2 into N(SiMe3)3

图15. 1,8-双(亚胺)咔唑支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 15. Synthesis of a cobalt-N2 complex supported by 1,8-bis(ketimino)carbazole and its application in catalyzing the conversion of N2 into N(SiMe3)3

Bond length d(N—N)/nm	IR ν(N—N)/cm^－1	TON^a	Bond length d(N—N)/nm	IR ν(N—N)/cm^－1	TON^a
0.1116(5)	2062	41	0.1128(3)~0.1150(3)	1837 1931	89
0.1154(2) 0.1159(3)	1807 1881	107(16)	0.1115(9)	2009	351(42)
0.1115(2)	2061	52	0.1121(3)	2103	329(11)

表1. 代表性的单核钴氮气配合物N—N键的键长和红外伸缩振动频率及其催化氮气到三(三甲基硅基)胺的转化数总结

Table 1. Summary of the N—N bond lengths and stretching frequencies of representative mononuclear cobalt-N2 complexes and the number of turnovers for their catalytic conversion of N2 into N(SiMe3)3

图16. 七齿N4P3配体支撑的双核钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 16. Synthesis of dicobalt complexes supported by heptadentate N4P3 ligand and their application in catalyzing the conversion of N2 into N(SiMe3)3

图17. 七齿N4P3配体支撑的双核钴配合物催化氮气分子转化为三(三甲基硅基)胺的可能途径

Figure 17. Possible route for the catalytic conversion of N2 into N(SiMe3)3 by dicobalt complexes supported by heptadentate N4P3 ligand

图18. 三(β-二亚胺)环芳烃支撑的三核钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 18. Synthesis of tricobalt complexes supported by tris(β-diketiminate) cyclophane and their application in catalyzing the conversion of N2 into N(SiMe3)3

图19. 吡唑桥联的双重钳形配体支撑的双核钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 19. Synthesis of dicobalt complexes supported by pyrazolate-based pincer ligand and their application in catalyzing the conversion of N2 into N(SiMe3)3

图20. 环戊二烯基-膦支撑的双核钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 20. Synthesis of dicobalt-N2 complexes supported by cyclopentadienyl-phosphine and their application in catalyzing the conversion of N2 into N(SiMe3)3

图21. 膦桥联的双核钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 21. Synthesis of a phosphido-bridged dicobalt complex and its application in catalyzing the conversion of N2 into N(SiMe3)3

图22. 稀土金属配体支撑的钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 22. Synthesis of cobalt-N2 complexes supported by rare- earth metal-based metalloligands and their application in cataly- zing the conversion of N2 into N(SiMe3)3

图23. 含双(吡啶二亚胺)的大环配体支撑的双核钴配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 23. Synthesis of dicobalt complexes supported by 3PDI2 macrocycle and their application in catalyzing the conversion of N2 into N(SiMe3)3

图24. 吡唑桥联的双(β-二亚胺)配体支撑的双核钴氮气配合物的合成及催化氮气到三(三甲基硅基)胺的转化

Figure 24. Synthesis of a dicobalt-N2 complex supported by pyrazolate-based di(β-diketiminate) and its application in catalyzing the conversion of N2 into N(SiMe3)3

Bond length d(N—N)/nm	IR ν(N—N)/cm^－1	TON^a
0.1114(4)	1994	178(37)
0.1124(3) 0.1125(3)	2032 2009	240
0.1138(3)	2044	53
0.1135(9) 0.1144(10)	1901	200

表2. 代表性的双核钴氮气配合物N—N键的键长和红外伸缩振动频率及其催化氮气到三(三甲基硅基)胺的转化数总结

Table 2. Summary of the N—N bond lengths and stretching frequencies of representative dinuclear cobalt-N2 complexes and the number of turnovers for their catalytic conversion of N2 into N(SiMe3)3

图25. 四齿BP3配体支撑的钴配合物的合成及催化氮气到氨气的转化

Figure 25. Synthesis of cobalt complexes supported by tetradentate BP3 ligand and their application in catalyzing the conversion of N2 into NH3

图26. PNP钳形配体支撑的钴配合物的合成及催化氮气到氨气的转化

Figure 26. Synthesis of cobalt complexes supported by PNP pincer ligand and their application in catalyzing the conversion of N2 into NH3

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