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

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.