Synthesis, characterization and electrocatalysis of diiron propanediselenolate derivatives as the active site models of [FeFe]-hydrogenases.

摘要: Abstract As an extension of our study on the H-cluster model compounds, a series diiron propanediselenolate (PDS)-type models have been successfully synthesized. Reaction diselenol HSe(CH 2 ) 3 SeH with Fe (CO) 12 in THF (tetrahydrofuran) at reflux gave parent compound [ μ -Se(CH Se- ]Fe 6 ( 1 48% yield. Further reaction PPh or H presence Me NO MeCN room temperature afforded phosphine-monosubstituted compounds 5 (L) , L  = PPh ; H) 76% and 68% yields, respectively. Similarly, N-heterocyclic carbene I Mes -monosubstituted (I 4 could be prepared 46% yield by imidazolium salt  · HCl n -BuLi followed treatment resulting ligand temperature. Compounds 1–4 were fully characterized elemental analysis various spectroscopic methods. While structures further confirmed X-ray crystallography, comparative its analog -S(CH S- demonstrates that is better catalyst for TsOH proton reduction to hydrogen under electrochemical conditions.