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Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand
Chinese Chemical Letters ( IF 9.4 ) Pub Date : 2023-11-11 , DOI: 10.1016/j.cclet.2023.109292
Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi

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

中文翻译:

非对称钳配体负载钴二氮配合物的合成及反应活性

合成并表征了非对称PNN钳配体[6-(BuPNH)CHN-2-(3-Mes)CHN]及其相应的钴-N配合物。通过PNN配体锂盐与CoCl的化学计量反应,得到配合物(PNN)CoCl。然后,在氮气气氛下用NaBHEt还原产生络合物,(PNN)Co(I)(-N)。单晶X射线分析、红外光谱和DFT计算表明,其中的二氮仅被钴中心微弱还原。与一氧化碳和2,6-二甲基苯基异氰化物反应分别生成羰基和异氰化物络合物 和 并释放出N。此外,这些钴配合物,尤其是配合物,表现出以中等效率将二氮转化为N(TMS)的能力。
更新日期:2023-11-11
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