Pendant bases as proton transfer relays in diiron dithiolate complexes inspired by Fe-Fe hydrogenase active site

• Three dinuclear iron complexes containing pendant nitrogen bases in phosphine ligands with general formular ( l- pdt) [ Fe2( CO) 5L] ( where pdt is SCH2CH2CH2S, L = PPh2NH( CH2) 2N( CH3) 2 ( 5), PPh2NH( 2- NH2C6H4) ( 6), PPh2[ 2- N( CH3) 2CH2C6H4] ( 7)), were prepared as the models of the [ Fe - Fe] hydrogenase active site. The molecular structures of 5 - 7 were characterized by X- ray crystallography. The secondary amine in 6 has weak intramolecular hydrogen bonding with both the terminal nitrogen and sulfur atom, which may suggest a proton transfer pathway from amine in phosphine ligand to the sulfur atom of active site. Protonation of complexes 5 and 6 only occurred at the terminal nitrogen atom. Electrochemical properties of the complexes were studied in the presence of tri. ic acid by cyclic voltammetry.

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