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

作     者：Yuanjin Chen Xianghui Shi Dajiang Huang Junnian Wei Zhenfeng Xi Yuanjin Chen;Xianghui Shi;Dajiang Huang;Junnian Wei;Zhenfeng Xi

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of EducationCollege of ChemistryPeking UniversityBeijing 100871China State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryShanghai 200032China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2024年第35卷第7期

页      面：259-263页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.21988101 and 22201013) Beijing Natural Science Foundation(No.2222008) supported by the High-performance Computing Platform of Peking University 

主　　题：Dinitrogen fixation Dinitrogen transformation Nonsymmetrical pincer ligand Cobalt complex Catalytic silylamine formation 

摘      要：A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and *** the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was ***,reduction of 3 with NaBHEt3under a dinitrogen atmosphere yielded complex 5,(PNN)Co(Ⅰ)(η^(1)-N_(2)).Single-crystal X-ray analysis,IR spectrum,and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt *** reactions of 5 with carbon monoxide and 2,6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N_(2),***,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.