Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases.
Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases.
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DOI：
10.1039/c5dt00067j
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发表时间：
2015-04
影响因子：
4
通讯作者：
Li-Cheng Song;Meng Cao;Yong-Xiang Wang
中科院分区：
文献类型：
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作者：
Li-Cheng Song;Meng Cao;Yong-Xiang Wang
由原位生成的Li_2 [Ni（1，2-S_2C_6H_4）_2]与2，6-双[（对甲苯磺酰氧基）甲基]吡啶及其取代衍生物2，6-双[（对甲苯磺酰氧基）甲基]-4-R-吡啶反应，合成了同双核配合物[Ni（RNPyS_4）]_2（RNPyS_4 = 2，6-双（2-巯基苯硫甲基）-4-R-吡啶; R = H，MeO，Cl，Br，i-Pr）.进一步与Fe_3（CO）_（12）反应，意外地得到了异三核配合物NiFe_2（RNPyS_4）（CO）_5（）和单核配合物Fe（RNPyS_4）（CO）（）。有趣的是，配合物和可以被视为模型的[NiFe]-和[Fe]-氢化酶的活性位点，分别。所有制备的配合物，其特征在于通过元素分析，光谱学，特别是其中的一些，通过X-射线晶体学。此外，利用循环伏安技术研究了和的电化学性质以及和的电催化制氢性能。
The homodinuclear complexes [Ni(RNPyS4)]2 (; RNPyS4 = 2,6-bis(2-mercaptophenylthiomethyl)-4-R-pyridine; R = H, MeO, Cl, Br, i-Pr) were found to be prepared by reactions of the in situ generated Li2[Ni(1,2-S2C6H4)2] with 2,6-bis[(tosyloxy)methyl]pyridine and its substituted derivatives 2,6-bis[(tosyloxy)methyl]-4-R-pyridine. Further reactions of with Fe3(CO)12 gave both heterotrinuclear complexes NiFe2(RNPyS4)(CO)5 () and mononuclear complexes Fe(RNPyS4)(CO) (), unexpectedly. Interestingly, complexes and could be regarded as models for the active sites of [NiFe]- and [Fe]-hydrogenases, respectively. All the prepared complexes were characterized by elemental analysis, spectroscopy, and particularly for some of them, by X-ray crystallography. In addition, the electrochemical properties of and as well as the electrocatalytic H2 production catalyzed by and were investigated by CV techniques.