Abstract
According to the remarkable efficiency of the hydrogenase model compound with phosphine bridging ligands, we have synthesized a series of hydrogenase model compounds containing sulfur or nitrogen bridging ligands. They are characterized by FTIR spectroscopy, NMR spectroscopy, electrochemistry and X-ray single crystallography. ([PPN][(μ-bdt)(μ-L)Fe2(CO)5] ; L = SPh (1)、SEt (2)、StBu (3)、pyrazole (4)) The complex 1-4 can be protonated by strong acid, such as HOTf, to form the species containing bridging hydrides. These hydride species are characterized by FTIR spectroscopy and are investigated by DFT calculation. Studying reduction of the hydride species allows us to propose the electrocatalytic mechanism for hydrogen formation.