含膦配体二铁二硫五羰基配合物的合成、表征及电催化产氢性能  

Synthesis,characterization,and electrocatalytic hydrogen evolution of diiron dithiolato pentacarbonyl complexes bearing phosphine ligand

作　　者：刘旭锋[1,2] 徐博 徐航 李玉龙 LIU Xu-Feng;XU Bo;XU Hang;LI Yu-Long(School of Materials and Chemical Engineering,Ningbo University of Technology,Ningbo,Zhejiang 315211,China;Zhejiang Institute of Tianjin University,Ningbo,Zhejiang 315201,China;College of Chemistry and Environmental Engineering,Sichuan University of Science&Engineering,Zigong,Sichuan 643000,China)

机构地区：[1]宁波工程学院材料与化学工程学院,宁波315211 [2]天津大学浙江研究院,宁波315201 [3]四川轻化工大学化学与环境工程学院,自贡643000

出　　处：《无机化学学报》2023年第8期1619-1627,共9页Chinese Journal of Inorganic Chemistry

基　　金：浙江省自然科学基金(No.LY19B020002);钒钛资源综合利用四川省重点实验室项目(No.2021FTSZ07);化学合成与污染控制四川省重点实验室项目(No.CSPC201904);四川省人社厅项目;四川轻化工大学项目(No.CX2021055)资助。

摘　　要：本文报道了4个含膦配体二铁二硫五羰基配合物的合成和结构表征。起始配合物[Fe_(2)(CO)_(6)(μ-SCH_(2)CH(CH_(2)OOCH)S)](1)与三苯基膦、三环己基膦、三(2-甲氧基苯基)膦或三(4-三氟甲基苯基)膦和脱羰试剂Me3NO·2H_(2)O反应,以59%~88%的产率制备了目标产物[Fe_(2)(CO)_(5)(L)(μ-SCH_(2)CH(CH_(2)OOCH)S)](L=PPh_(3)(2)、PCy_(3)(3)、P(2-C_(6)H_(4)OCH_(3))_(3)(4)、P(4-C_(6)H_(4)CF_(3))_(3)(5))。配合物2~5以元素分析、红外光谱、核磁共振以及单晶X射线衍射进行了表征。电化学性质研究表明配合物1~5均可以实现电化学催化质子还原产生氢气的功能,其中配合物1的催化产氢效率明显优于其它配合物。In this work,four diiron dithiolato pentacarbonyl complexes with phosphine ligands were synthesized and structurally characterized.The starting complex[Fe_(2)(CO)_(6)(μ-SCH_(2)CH(CH_(2)OOCH)S)](1)reacted with triphenylphos-phine,tricyclohexylphosphine,tris(2-methoxyphenyl)phosphine,or tris(4-(trifluoromethyl)phenyl)phosphine and Me_(3)NO·2H_(2)O as the decarbonylation agent to produce the target products[Fe_(2)(CO)_(5)(L)(μ-SCH_(2)CH(CH_(2)OOCH)S)](L=PPh_(3)(2),PCy_(3)(3),P(2-C_(6)H_(4)OCH_(3))_(3)(4),P(4-C_(6)H_(4)CF_(3))_(3)(5))in 59%-88% yields.Complexes 2-5 have been character-ized by elemental analysis,IR,and NMR spectroscopy,together with single-crystal X-ray diffraction analysis.Elec-trochemical studies have revealed that complexes 1-5 could electro-catalyze the reduction of proton to hydrogen and complex 1 had better catalytic efficiency than other complexes.CCDC:2225330,2;2225331,3;2225332,4‧CH_(2)Cl_(2);2225333,5.

关 键 词：铁铁氢化酶 双铁配合物 X射线晶体学 产氢催化剂 

分 类 号：O614.811[理学—无机化学]