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

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.