[FeFe]‐Hydrogenase Models Containing Long Diselenolato Linkers

Abstract

Reactions of Fe3(CO)12 with cyclic diselenides or diselenocyanatoalkanes produced two different products, namely the dinuclear [Fe2(CO)6{μ‐(SeCH2)2(CH2)n}] (n= 5 (1 a), 6 (1 b), 7 (1 c), 8 (1 d)) and the tetranuclear models [Fe2(CO)6{μ‐(SeCH2)2(CH2)n}]2 (n=5 (2 a), 6 (2 b), 7 (2 c), 8 (2 d)). The resulting complexes were fully characterized by a variety of analytical techniques (NMR spectroscopy, elemental analysis, mass spectrometry) and by X‐ray structure determination of complexes 1 c, 1 d, 2 c and 2 d. Furthermore, we investigated the redox properties and the catalytic behaviour of complexes 1 a‐d in the presence of acetic acid (AcOH) as a source of protons.

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

“…Similarly, the 31 Evidence for the number of electrons involved in the reduction of the complexes could be obtained from studying the scan rate dependence of the current function Ip/c.ν 1/2 (Ip = peak current, c = concentration, ν = scan rate). [62][63][64][65][66][67][68][69][70] While Ip/c.ν 1/2 decreases towards a constant value as the scan rate increases in the cases of 1 38 and 3, the current function is found to be scan rate independent for 2 ( Figure 5). These observations suggest an ECE cathodic process (E = Electron transfer and C = Chemical process) in the case of 1 and 3 while the reduction of 2 involves simple transfer of one electron.…”

Synthesis and Electrochemical Investigations of the [FeFe]‐Hydrogenase H‐Cluster Mimics Mediated by Bicyclic Dithiols Derivative

“…The anodic scan of complex 2 reveals an irreversible oxidation peak at E ox = + 0.89 V, this signal could be attributed to the one-electron oxidation process of Fe I Fe I !Fe I Fe II as formerly reported for various diiron complexes. [13,[41][42]…”

Influence of bidentate phosphine ligands on the chemistry of [FeFe]‐hydrogenase model: insight into molecular structures and electrochemical characteristics

“…These ranges are comparable to the ranges observed for similar systems. [25][26][27][28][29][30][31][32][33][34][35]43,44] The 77 Se{ 1 H} NMR spectra of complexes 2 and 3 presented a weak signal at 341.6 ppm for 2 and 252.1 ppm for 3 ( Figures S9, S13 NMR spectrum of 2 displayed four peaks of almost equal intensity at 44.7, 43.9, 42.7 and 41.72 ppm ( Figures S7). This finding was quiet unexpected and in contrast to the one singlet observed for [Fe 2 {μ-SCH 2 CH 2 CH 2 S-μ}(CO) 5 ] 2 {μ,κ 1 ,κ 1 (P,P)-dppac} or [Fe 2 {μ-SCH 2 CH 2 S-μ}(CO) 5 ] 2 {μ,κ 1 , κ 1 (P,P)-dppac} as reported.…”