Song Li-Cheng, Liu Bei-Bei, Liu Wen-Bo, Tan Zheng-Lei
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University Tianjin 300071 China
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Tianjin 300072 China.
RSC Adv. 2020 Aug 28;10(53):32069-32077. doi: 10.1039/d0ra04344c. eCollection 2020 Aug 26.
To develop the biomimetic chemistry of [NiFe]-Hases, the first azadithiolato-bridged NiFe model complexes [CpNi{(μ-SCH)NR}Fe(CO)(diphos)]BF (5, R = Ph, diphos = dppv; 6, 4-ClCH, dppv; 7, 4-MeCH, dppv; 8, COCHPh, dppe; 9, H, dppe) have been synthesized well-designed synthetic routes. Thus, treatment of RN[CHS(O)CMe] with -BuONa followed by reaction of the resulting intermediates RN(CHSNa) with (dppv)Fe(CO)Cl or (dppe)Fe(CO)Cl gave the N-substituted azadithiolato-chelated Fe complexes [RN(CHS)]Fe(CO)(diphos) (1, R = Ph, diphos = dppv; 2, 4-ClCH, dppv; 3, 4-MeCH, dppv; 4, COCHPh, dppe). Further treatment of 1-4 with nickelocene in the presence of HBF·EtO afforded the corresponding N-substituted azadithiolato-bridged NiFe model complexes 5-8, while treatment of 8 with HBF·EtO resulted in formation of the parent azadithiolato-bridged model complex 9. While all the new complexes 1-9 were characterized by elemental analysis and spectroscopy, the molecular structures of model complexes 6-8 were confirmed by X-ray crystallographic study. In addition, model complexes 7 and 9 were found to be catalysts for H production with moderate / and overpotential values from TFA under CV conditions.
为了开展[NiFe]-氢化酶的仿生化学研究，通过精心设计的合成路线，合成了首例氮杂二硫醇盐桥联的NiFe模型配合物[CpNi{(μ-SCH)NR}Fe(CO)(diphos)]BF（5，R = Ph，diphos = dppv；6，4-ClCH，dppv；7，4-MeCH，dppv；8，COCHPh，dppe；9，H，dppe）。因此，用叔丁醇钠处理RN[CHS(O)CMe]，然后将所得中间体RN(CHSNa)与(dppv)Fe(CO)Cl或(dppe)Fe(CO)Cl反应，得到N-取代氮杂二硫醇盐螯合的Fe配合物[RN(CHS)]Fe(CO)(diphos)（1，R = Ph，diphos = dppv；2，4-ClCH，dppv；3，4-MeCH，dppv；4，COCHPh，dppe）。在HBF·EtO存在下，用二茂镍进一步处理1-4，得到相应的N-取代氮杂二硫醇盐桥联的NiFe模型配合物5-8，而用HBF·EtO处理8则生成母体氮杂二硫醇盐桥联的模型配合物9。虽然所有新配合物1-9都通过元素分析和光谱进行了表征，但模型配合物6-8的分子结构通过X射线晶体学研究得到了证实。此外，发现模型配合物7和9在循环伏安条件下是从三氟乙酸中产生氢气的催化剂，具有适中的过电位值。
