Electrocatalytic Behavior of Tetrathiafulvalene (TTF) and Extended Tetrathiafulvalene (exTTF) [FeFe] Hydrogenase Mimics

Abstract

TTF-and exTTF-containing [(μ-S 2 )Fe 2 (CO) 6 ] complexes have been prepared by the photochemical reaction of TTF or exTTF and [(μ-S 2 )Fe 2 (CO) 6 ]. These complexes are able to interact with PAHs. In the absence of air and in acid media an electrocatalytic dihydrogen evolution reaction (HER) occurs, similarly to analogous [(μ-S 2 )Fe 2 (CO) 6 ] complexes. However, in the presence of air, the TTF and exTTF organic moieties strongly influence the electrochemistry of these systems. The reported data may be valuable in the design of [FeFe] hydrogenase mimics able to combine the HER properties of the [FeFe] cores with the unique TTF properties.

Heteropolymetallic [FeFe]-Hydrogenase Mimics: Synthesis and Electrochemical Properties

“…In this context, the linkers reported to join the [Fe 2 S 2 ] units are mere connectors between the electrochemically active diiron moieties, and, as far as we know, they have not been conceived for further modifications or reactivity studies. In our current research, we are interested in the development of methodologies for the incorporation of [FeFe]-hydrogenase mimics into diverse types of molecules. − Here, our approach focuses on the design of a polynuclear complex 6 with an active linker, suitable to facilitate the electronic communication between the [FeFe] centers and also able to act as a ligand to incorporate transition metal complexes in the structure (Figure ). The structure of 6 combines two [Fe 2 S 2 ] units, known to be electrocatalytically active for hydrogen production, with a π-conjugated linker that also has the chelating properties of the 2,2′-bipyridine moiety, a ligand widely employed in transition-metal coordination chemistry.…”