Abstract
Three dinuclear iron complexes containing pendant nitrogen bases in phosphine ligands with general formular (μ-pdt) [Fe 2(CO) 5L] (where pdt is SCH 2CH 2CH 2S, L = PPh 2NH(CH 2) 2N(CH 3) 2 ( 5), PPh 2NH(2-NH 2C 6H 4) ( 6), PPh 2[2-N(CH 3) 2CH 2C 6H 4] ( 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 triflic acid by cyclic voltammetry.
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