Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H-2 Evolution Catalyzed by [(mu-SeCH2)(mu-CH2NCH2Ph)]Fe-2(CO)(6)
Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H-2 Evolution Catalyzed by [(mu-SeCH2)(mu-CH2NCH2Ph)]Fe-2(CO)(6)
复制标题
含有蝶形 Fe/E（E = S、Se 或 Te）簇核心的 [FeFe]-氢化酶模型的合成和结构研究。
DOI：
10.1021/acs.organomet.9b00022
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Wang Yong-Xiang
中科院分区：
文献类型：
--
作者：
Song Li-Cheng;Chen Jin-Sen;Jia Guo-Jun;Wang Yong-Zhen;Tan Zheng-Lei;Wang Yong-Xiang
As models of [FeFe]-H2ases, 13 butterfly Fe/E (E = S, Se, or Te) complexes (1–13) have been prepared by various synthetic methods. Treatment of [(μ-SCH2)2CH2]Fe2(CO)6(A) and [(μ-SCH2)2CHO2CPh]Fe2(CO)6(B) with the in situ-generated N-heterocyclic carbenes (NHC) IMe/Mes, IVinyl/Mes, IMes, and IMegave the corresponding carbene-substituted butterfly [2Fe2S] complexes [(μ-SCH2)2CH2]Fe2(CO)5(IMe/Mes) (1), [(μ-SCH2)2CH2]Fe2(CO)5(IVinyl/Mes) (2), [(μ-SCH2)2CHO2CPh]Fe2(CO)5(IMes) (3), and [(μ-SCH2)2CHO2CPh]Fe2(CO)4(IMe)2(4), respectively. Although theN-p-methoxyphenyl-substituted 1,2,4-diselenazolidineCreacted with Fe3(CO)12to give the expected butterfly [2Fe2Se] complex [(μ-SeCH2)2NC6H4OMe-p]Fe2(CO)6(5) and further reaction of5with PPh3afforded its PPh3-substituted derivative [(μ-SeCH2)2NC6H4OMe-p]Fe2(CO)5(PPh3) (6), theN-arylmethyl-substituted 1,2,4-diselenazolidinesD–Freacted with Fe3(CO)12to give the first butterfly [2Fe1Se1N1C] complexes [(μ-SeCH2)(μ-CH2NR)]Fe2(CO)6(7, R = PhCH2;8, R = NC5H4CH2-p;9, R = CpFeC5H4CH2), unexpectedly. More interestingly, on the basis of synthesizing the first ODTe-bridged butterfly [2Fe2Te] complex [(μ-TeCH2)2O]Fe2(CO)6(10), the NHC-substituted butterfly [2Fe2Te] complexes [(μ-TeCH2)2O]Fe2(CO)5(L) (11, L = IMe/Mes;12, L = IMes;13, L = IMe) were prepared by reactions of complex10with the corresponding NHC ligands. In addition, while all of the new complexes1–13were structurally characterized, complex7was found to be a H2-producing catalyst from benzoic acid andp-toluenesulfonic acid under cyclic voltammetry conditions.
