Structural studies and electrochemical catalysis investigation of [FeFe]-hydrogenase H-cluster mimics mediated by monophosphane ligands

In this research work we present the reaction of the precursor complexes [Fe-2(CO)(6){mu-(SeCH2)(2)CMeR}] (R = H (1) or Me (2)) with monophosphine/phosphane ligands, PPh3 and P(OMe)(3), to afford the mono-substituted complexes [Fe-2(CO)(5)PPh3{mu-(SeCH2)(2)CHMe}] (3), [Fe-2(CO)(5)PPh3{mu-(SeCH2)(2)CMe2}] (4), [Fe-2(CO)(5)P (OMe)(3){mu-(SeCH2)(2)CHMe}] (5) and [Fe-2(CO)(5)P(OMe)(3){mu-(SeCH2)(2)CMe2}] (6). The structures of complexes 3-6 were confirmed by X-ray diffraction analysis. Moreover, we studied the influence of the steric interference of the mu-Se-to-Se linker with the nearby ligands (PPh3 and P(OMe)(3)) on the electronic properties, the solid-state structures and the mechanism of the cathodic process of complexes 3-6 compared to that of 1 and 2. In addition, a detailed electrochemical study of complexes 3-6 in the absence and presence of acetic acid AcOH, is also reported.

Automated summary

The research focused on the reaction of precursor complexes with monophosphine/phosphane ligands, resulting in mono-substituted complexes whose structures were confirmed through X-ray diffraction analysis. It also examined the influence of the steric interference of the mu-Se-to-Se linker on the electronic properties of the complexes, solid-state structures, and cathodic process, as well as conducting detailed electrochemical studies in the presence and absence of acetic acid.