Details

Autor(en) / Beteiligte

• Hu, Shu-Peng
• Zhang, Li
• Wu, Yu
• Feng, Jian-Shen
• Wu, Sheng
• Xie, Bin
• Zou, Li-Ke

Titel

[FeFe]-hydrogenase active site mimics containing pyridyl-functionalized phosphine ligands: Synthesis, characterization and electrochemical investigation

Ist Teil von

• Inorganica Chimica Acta, 2020-05, Vol.504, p.119435, Article 119435

Ort / Verlag

Amsterdam: Elsevier B.V

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• As the active site models of [FeFe]-H2ase, three dinuclear iron complexes containing pyridyl-functionalized phosphine ligands, [(μ-EDT)Fe2(CO)5(Ph2PPy-4)] (1), [(μ-EDT)Fe2(CO)5 (Ph2PCH2Py-4)] (2), [(μ-PDT)Fe2(CO)5(Ph2PCH2Py-4)] (3) (Py = pyridyl ring, EDT = SCH2CH2S and PDT = SCH2CH2CH2S), were prepared and characterized by IR, NMR spectroscopies and X-ray crystallography. Electrochemical studies show that the newly synthesized model complexes are potential candidates for electrocatalytic H2 evolution. The results of UV–Vis titrations indicate that photosensitizer ZnTPP and 1 are readily self-assembled into a supramolecular dyad via noncovalent axial coordination in CH2Cl2. [Display omitted] •Pyridyl-functionalized mimics of [FeFe]-H2ase active site 1–3 have been synthesized.•1–3 exhibit electrocatalytic activities for H2 evolution in HOAc/HCN.•1–3 can self-assemble into supra-molecular dyad with photosensitizer ZnTPP. Three dinuclear iron complexes containing pyridyl-functionalized phosphine ligands, [(μ-EDT)Fe2(CO)5(Ph2PPy-4)] (1), [(μ-EDT)Fe2(CO)5 (Ph2PCH2Py-4)] (2), [(μ-PDT)Fe2(CO)5(Ph2PCH2Py-4)] (3) (where Py is pyridyl ring, EDT is SCH2CH2S, PDT is SCH2CH2CH2S), were prepared as the active site models of [FeFe]-hydrogenases. The molecular structures of 1–3 were fully characterized by IR and NMR (1H, 13C, 31P) spectroscopies and X-ray crystallography. The electrochemical properties of 1–3 in CH3CN were investigated by cyclic voltammetry in the presence of acetic acid and found to be potential candidates for electrocatalytic H2 evolution. In addition, the self-assembling behavior of 1 with zinc tetraphenylporphyrin (ZnTPP) was studied by UV–vis spectroscopy.