| 两个含氨基膦配体的二铁配合物的合成、表征与电催化产氢活性 |
| Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine |
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| 摘要: 为开发新型的铁铁氢化酶模拟物，我们合成并表征了2个含氨基膦配体的二铁配合物。配合物[Fe2(CO)6(μ-pdt)] (1)(pdt=SCH2CH2CH2S)与双膦配体(Ph2PCH2)2NC10H15 (dppad)和 Me3NO·2H2O 反应得到了主产物(60% 产率)[Fe2(CO)5(mpad)(μ-pdt)] (2)和副产物(6%产率)[Fe2(CO)4(κ2-dppad)(μ-pdt)] (3)，其中mpad=Ph2PCH2NHC10H15。配合物2和3以元素分析、红外光谱、核磁共振 1H和 31P波谱、单晶X射线衍射进行表征。此外，用循环伏安法研究了配合物2和3的电化学和电催化产氢活性，结果表明在有醋酸作为质子源的条件下，配合物2和3均可以催化质子还原生成氢气。其中，配合物3的催化效率(转换频率)要稍微优于配合物2。 |
| 关键词: 铁铁氢化酶 双膦 晶体结构 电催化产氢 |
| 基金项目: 浙江省自然科学基金(No.LY19B020002)资助。 |
| Abstract: To explore new biomimics for the [FeFe]-hydrogenases active site, two di-iron complexes containing a phosphine ligand with a pendant amine were synthesized and characterized. Reaction of complex [Fe2(CO)6(μ-pdt)] (1), where pdt=SCH2CH2CH2S, with a diphosphine ligand (Ph2PCH2)2NC10H15 (dppad) and Me3NO·2H2O gave a major product [Fe2(CO)5(mpad)(μ-pdt)] (2) in 60% yield together with a minor product [Fe2(CO)4(κ2-dppad)(μ-pdt)] (3) in 6% yield, where mpad=Ph2PCH2NHC10H15. Complexes 2 and 3 were identified by elemental analysis, IR, 1H NMR, 31P NMR, and single-crystal X-ray diffraction analysis. The crystal structure of complex 2 contains an apicallycoordinated phosphine ligand mpad whereas complex 3·0.5CH2Cl2 contains a chelated diphosphine ligand dppad in an apical-basal position. The Fe-Fe bond length in complex 2 [0.251 66(6) nm] is notably shorter than that in complex 3·0.5CH2Cl2 [0.255 88(6) nm]. Furthermore, the electrochemical properties of complexes 2 and 3 were investigated by cyclic voltammetry (CV), revealing that their CV curves contained two reduction peaks and one oxidation peak within the solvent window. The electrocatalytic properties of both complexes showed that they can catalyze the reduction of protons to H2 with HOAc as a proton source. For comparison, the catalytic efficiency (turnover frequency) of 3 was slightly better than that of 2. |
| Keywords: [FeFe]-hydrogenases diphosphine crystal structure electrocatalytic hydrogen evolution |
| 投稿时间：2024-11-22 修订日期：2025-02-27 |
| 摘要点击次数: 199 |
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| 朱霖洁,刘旭锋.两个含氨基膦配体的二铁配合物的合成、表征与电催化产氢活性[J].无机化学学报,2025,41(5):939-947. |
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