Citation: Yuanjin Chen, Xianghui Shi, Dajiang Huang, Junnian Wei, Zhenfeng Xi. Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand[J]. Chinese Chemical Letters, ;2024, 35(7): 109292. doi: 10.1016/j.cclet.2023.109292 shu

Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand

Yuanjin Chen ^a ,
Xianghui Shi ^a ,
Dajiang Huang ^a ,
Junnian Wei ^{a, *,} ,
Zhenfeng Xi ^{a, b, *,}

a.
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China

jnwei@pku.edu.cn

zfxi@pku.edu.cn

Received Date: 9 August 2023
Revised Date: 29 October 2023
Accepted Date: 9 November 2023
Available Online: 11 November 2023

Figures(9)

A nonsymmetrical PNN pincer ligand [6-(Bu₂PNH)C₅H₄N-2-(3-Mes)C₃H₂N₂] and its corresponding cobalt-N₂ complex were synthesized and characterized. By the stoichiometric reaction of the PNN ligand lithium salt with CoCl₂, the complex 3, (PNN)CoCl, was obtained. Then, reduction of 3 with NaBHEt₃ under a dinitrogen atmosphere yielded complex 5, (PNN)Co(Ⅰ)(η¹-N₂). Single-crystal X-ray analysis, IR spectrum, and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center. The reactions of 5 with carbon monoxide and 2, 6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N₂, respectively. Furthermore, these cobalt complexes, especially complex 5, demonstrated the capacity to convert dinitrogen to N(TMS)₃ with moderate efficiency.
- Dinitrogen fixation,
- Dinitrogen transformation,
- Nonsymmetrical pincer ligand,
- Cobalt complex,
- Catalytic silylamine formation
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