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

[Image: see text] 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.