Novel [FeFe]-Hydrogenase Mimics: Unexpected Course of the Reaction of Ferrocenyl α-Thienyl Thioketone with Fe3(CO)12

Abstract

The influence of the substitution pattern in ferrocenyl α-thienyl thioketone used as a proligand in complexation reactions with Fe₃(CO)₁₂ was investigated. As a result, two new sulfur-iron complexes, considered [FeFe]-hydrogenase mimics, were obtained and characterized by spectroscopic techniques (¹H, ¹³C{¹H} NMR, IR, MS), as well as by elemental analysis and X-ray single crystal diffraction methods. The electrochemical properties of both complexes were studied and compared using cyclic voltammetry in the absence and in presence of acetic acid as a proton source. The performed measurements demonstrated that both complexes can catalyze the reduction of protons to molecular hydrogen H₂. Moreover, the obtained results showed that the presence of the ferrocene moiety at the backbone of the linker of both complexes improved the stability of the reduced species.