Research Progress on Catalytic Dinitrogen Activation and Functionalization Mediated by Cobalt Complexes

doi:10.6023/cjoc202602020

Abstract

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

Cite this article

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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Fig. & Tab. 28

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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)

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

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

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

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

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

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

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

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

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

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

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

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

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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