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

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

机构地区：[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]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Shanghai 200032,China

出　　处：《Chinese Chemical Letters》2024年第7期259-263,共5页中国化学快报（英文版）

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。

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 characterized.By the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was obtained.Then,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 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 N_(2),respectively.Furthermore,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.

关 键 词：Dinitrogen fixation Dinitrogen transformation Nonsymmetrical pincer ligand Cobalt complex Catalytic silylamine formation 

分 类 号：O641.4[理学—物理化学]