Electrocatalytic hydrogen production using [FeFe]-hydrogenase mimics based on tetracene derivatives

Abstract

The synthesis, structure, physical properties, and electrocatalytic hydrogen production of tetrathiatetracene ligand based [FeFe]-hydrogenase mimic molecules were investigated.

Ligand effects on structural, protophilic and reductive features of stannylated dinuclear iron dithiolato complexes

“…14 For several years, extensive efforts have been devoted to designing structural and functional models so as to mimic the protonation and redox properties of the H-cluster. [15][16][17][18][19][20][21][22][23][24] These models include a variety of dithiolato ligands, μ-(SCH2)2X, in which the central atom/group X could be NR, CR2, O, S, SnR2 or (Ph)P=O ( Figure 1B). [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] Moreover, several research groups have reported approaches for introducing strong σ-donor ligands, such as phosphines and phosphites, at the diiron core to enhance the protophilicity of the model complexes ( Figure 1B).…”

Electrochemical Behavior of Mono‐Substituted [FeFe]‐Hydrogenase H‐Cluster Mimic Mediated by Stannylated Dithiolato Ligand

“…During the last few decades, numerous synthetic approaches have been designed to mimic the protonation and redox properties of the natural archetype [19–33] . It is worth pointing out that the nature of the central atom/group in the bridging dithiolato linkers has a significant role in determining the electronic/steric properties of such artificial H‐cluster mimics [34–38] .…”

“…[14][15][16][17][18] During the last few decades, numerous synthetic approaches have been designed to mimic the protonation and redox properties of the natural archetype. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] It is worth pointing out that the nature of the central atom/group in the bridging dithiolato linkers has a significant role in determining the electronic/steric properties of such artificial H-cluster mimics. [34][35][36][37][38] For example, the presence of group 14 elements at the bridgehead atom of [Fe 2 (CO) 6 {μ-(SCH 2 ) 2 EMe 2 }] (E = C, Si, Ge and Sn) complexes results in increasing the electron density at the FeÀ Fe vector.…”

Ligand Effects on Structural, Protophilic and Reductive Features of Stannylated Dinuclear Iron Dithiolato Complexes

“…For several years, extensive efforts have been devoted to designing structural and functional models so as to mimic the protonation and redox properties of the H-cluster. [15][16][17][18][19][20][21][22][23][24] These models include a variety of dithiolato ligands, μ-(SCH2)2X, in which the central atom/group X could be NR, CR2, O, S, SnR2 or (Ph)P=O (Figure 1B). [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] Moreover, several research groups have reported approaches for introducing strong σ-donor ligands, such as phosphines and phosphites, at the diiron core to enhance the protophilicity of the model complexes (Figure 1B).…”