Synthetic and structural study on some new porphyrin or metalloporphyrin macrocycle-containing model complexes for the active site of [FeFe]-hydrogenases

•Synthesis of the first porphyrinylester-containing H-cluster models.•Synthesis of the first porphyrinylthioether-containing H-cluster models.•Four crystal structures are reported.•DFT computations on one model are performed.

To mimick the natural enzymes [FeFe]-hydrogenases, some new porphyrin and metalloporphyrin moiety-containing model complexes, namely 5-[p-Fe2(CO)6(μ-SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrin (2), 5-[p-Fe2(CO)6(μ-SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrinozinc (3), 5-[p-Fe2(CO)6(μ-SCH2)2NC2H4SC6H4],10,15,20-triphenylporphyrin (7), and 5-[p-Fe2(CO)5(μ-SCH2)2NC2H4SC6H],10,15,20-triphenylporphyrin (8), have been successfully prepared by our designed synthetic routes involving the corresponding precursor compounds [(μ-SCH2)2CHO2CC6H4CHO-p]Fe2(CO)6 (1), p-Boc-NHC2H4SC6H4CHO (4), 5-(p-Boc-NHC2H4SC6H4),10,15,20-triphenylporphyrin (5), and 5-(p-NH2C2H4 SC6H4),10,15,20-triphenylporphyrin (6). All these new compounds 1–8 have been characterized by elemental analysis and various spectroscopic methods, and particularly for 1–3 and 7 by X-ray crystallography. In addition, the density functional theory computations on 8 were performed to assist its structural characterization.

Graphical abstractSome new porphyrin or metalloporphyrin moiety-containing H-cluster models, such as 3 and 8, have been prepared and their structures are fully characterized by elemental analysis, spectroscopy, and X-ray crystallography or DFT computations.Figure optionsDownload full-size imageDownload as PowerPoint slide