871565-41-2

Upstream product

• 615250-43-6 [{(μ-SCH₂)₂O}Fe₂(CO)₆] 
• 603-35-0 triphenylphosphine 
• 75-05-8 acetonitrile 

Relevant academic research and scientific papers

Phosphine-substituted diiron complexes Fe2(μ-Rodt)(CO)6?n(PPh3)n(R = Ph, Me, H andn= 1, 2) featuring desymmetrized oxadithiolate bridges: structures, protonation, and electrocatalysis

Two new series of phosphine-substituted diiron complexes Fe2(μ-Rodt)(CO)6?n(PPh3)n(n= 1 for4-6andn= 2 for7-9) bearing desymmetrized oxadithiolate bridges (i.e., Rodt bridges), which can be considered as diiron subsite models of [FeFe]-hydrogenases, were prepared through the Me3NO-induced replacements of all-CO diiron precursors Fe2(μ-Rodt)(CO)6(Rodt = SCH(R)OCH2S; R = Ph (1), Me (2), and H (3)) with one equivalent or excess PPh3. All the as-obtained complexes have been fully characterized by elemental analysis, various spectroscopy methods, and especially for4,7-9by X-ray crystallography. Further protonation and electrochemistry of4-6and7-9with Rodt bridges are studied and compared without and with CF3CO2H (TFA) and CH3CO2H (HOAc) as strong and weak acidic proton sources byin situIR plus NMR spectroscopies and cyclic voltammetry. On the one hand, under excess TFA, the monosubstituted complexes4-6are partially protonated to produce a mixture of main precursors4-6and minor Fe-protonated species[4(μH)]+,[5(μH)]+, and[6(μH)]+, whereas the disubstituted counterparts7-9are completely protonated to form an isomeric mixture of their hydride species[7(μH)]+,[8(μH)]+, and[9(μH)]+intransoid-dibasal and apical-basal fashions. On the other hand, complexes7-9show better electrocatalytic proton reduction activities (i.e., higher turnover numbers/TONs) under TFA or HOAc relative to counterparts4-6, in which the TONs of4,5and7,8with Phodt or Meodt bridges are a little higher than those of6and9with odt bridges, respectively. These findings reveal that the redox and electrocatalytic behaviors of4-6and7-9with Rodt bridges are affected not only by phosphine coordination modes (PPh3, mono-vs.di-substitution) but also by desymmetrized dithiolate bridges (Rodt, R = Ph, Mevs.H).

Diiron oxadithiolate type models for the active site of iron-only hydrogenases and biomimetic hydrogen evolution catalyzed by Fe 2(μ-SCH2OCH2S-μ)(CO)6

The biomimetic chemistry of single and double oxadithiolatodiiron- containing model compounds for the active site of Fe-only hydrogenases (FeHases) has been systematically studied. The simplest such model, Fe 2(μ-SCH2OCH2S