通过配体取代反应合成了2个双膦配体桥联的四铁配合物[Fe₄(CO)₁₀(μ-SCH₂CH (CH₃) S)₂(dppa)](1)和[Fe₄(CO)₁₀(μ-SCH₂CH (CH₃) S)₂(trans-dppv)](2)，其中dppa=双(二苯基膦)乙炔，trans-dppv=trans-1，2-双(二苯基膦)乙烯。配合物的结构经过元素分析、红外光谱、核磁共振氢谱、磷谱以及单晶X射线衍射等方法的表征。用循环伏安法研究了新配合物的电化学性质，结果表明它们均可以在乙腈溶液中催化醋酸中的质子还原产生氢气。其中配合物2的催化效率要明显优于配合物1。

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(κ^2-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。

To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H₂) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe₂(μ-X₂pdt)(CO)₆] (X₂pdt=(SCH₂)₂CX₂, X=Me, H) with aminodiphosphines (Ph₂PCH₂)₂NY(Y=(CH₂)₂OH, (CH₂)₃OH) to obtain two new diiron aminophosphine complexes [Fe₂(L1)(μ-Me₂pdt)(CO)₅] (1) and [Fe₂(L2)(μ-H₂pdt)(CO)₅] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H₂ generation in the presence of HOAc.

This paper reports the preparation of three di-iron complexes containing a thiazole moiety. Esterification of complex [Fe₂(CO)₆(μ-SCH₂CH(CH₂OH)S)] (1) with 4-methylthiazole-5-carboxylic acid gave the corresponding ester [Fe₂(CO)₆(μ-tedt)] (2), where tedt=SCH₂CH(CH₂OOC(5-C₃HNSCH₃))S. Further reactions of complex 2 with tri(p-tolyl)phosphine (tp) or tris(4-fluorophenyl)phosphine (fp) gave the phosphine-substituted derivatives [Fe₂(CO)₅(tp)(μ-tedt)] (3) and [Fe₂(CO)₅(fp)(μ-tedt)] (4). The structures of the newly prepared complexes were elucidated by elemental analysis, NMR, IR, and X-ray photoelectron spectroscopy. Moreover, single-crystal X-ray diffraction analysis confirmed their molecular structures, showing that they contain a di-iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls. The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry, revealing that three complexes can catalyze the reduction of protons to H₂ under the electrochemical conditions. For comparison, complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^-1 at 10 mmol·L^-1 HOAc concentration. In addition, the fungicidal activity of these complexes was also investigated in this study.