Synthesis, structures and electrochemical properties of hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes

• The hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes [[(mu-SCH2)(2)N(CH2CH2OH)}Fe-2(CO)(6)] (1) and [{(mu-SCH2)(2)N(CH2CH2OOCPy)} Fe-2(CO)(6)] (Py = pyridyl) (2) were prepared as biomimetic models of the active site of Fe-only hydrogenases. Both complexes were characterized by MS, IR, H-1 NMR spectra and elemental analysis. The molecular structures of 1 and 2 were determined by single crystal X-ray analysis. A network is constructed by intermolecular H-bonds in the crystals of 1. An S center dot center dot center dot O intermolecular contact was found in the crystals of 2, which is scarcely found for organometallic complexes. Cyclic voltammograms of 1 and 2 were studied to evaluate their redox properties.

Nyckelord

azapropanedithiolate

bioinorganic chemistry

diiron complex

iron-only hydrogenase

S center dot center dot center dot O intermolecular contact

hydrogenase active-site

fe-only hydrogenase

all-iron hydrogenase

desulfovibrio-desulfuricans

ruthenium photosensitizer

crystal-structures

biomimetic model

coordination

evolution

sulfides

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