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

Yuanjin Chen ¹Xianghui Shi ¹Dajiang Huang ¹Junnian Wei ¹Zhenfeng Xi²

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作者信息

1. 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
2. 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;State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Shanghai 200032,China
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Abstract

A nonsymmetrical PNN pincer ligand[6-(tBu2PNH)C5H4N-2-(3-Mes)C3H2N2]and its corresponding cobalt-N2 complex were synthesized and characterized.By the stoichiometric reaction of the PNN lig-and 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)(η 1-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 effi-ciency.

Key words

Dinitrogen fixation/Dinitrogen transformation/Nonsymmetrical pincer ligand/Cobalt complex/Catalytic silylamine formation

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基金项目

National Natural Science Foundation of China(21988101)

National Natural Science Foundation of China(22201013)

Beijing Natural Science Foundation(2222008)

Highperformance Computing Platform of Peking University()

出版年

2024

中国化学快报(英文版)

中国化学会

中国化学快报(英文版)

CSTPCD

影响因子：0.771

ISSN：1001-8417

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