Investigations on the PNP‐chelated diiron dithiolato complexes Fe2(μ‐edt)(CO)4{κ2‐(Ph2P)2NC6H4R} related to the [FeFe]‐hydrogenase active site. Issue 6 (29th January 2021)

• Record Type: Journal Article
• Authors: Lü, Shuang; Tian, Wen‐Jing; Xu, Ting‐Ting; Yang, Jun; Li, Qian‐Li; Li, Yu‐Long
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 647:Issue 6(2021)
• Page Start: 618
• Page End: 622
• Publication Date: 2021-01-29
• Subjects: Hydrogenase -- facile synthesis -- aminodiphosphine ligand -- X-ray crystallography -- electrochemistry; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.202000353
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract: The chemistry of the diiron dithiolato hexacarbonyl complex Fe2 (μ‐edt)(CO)6 (edt, 1, 2‐ethanedithiolate) has received special attention, largely because that its structure is similar with the active site of [FeFe]‐hydrogenase. In order to enrich the chemistry of complex Fe2 (μ‐edt)(CO)6 and synthesize new hydrogen evolution catalysts, a new route to the diiron dithiolato hexacarbonyl complex Fe2 (μ‐edt)(CO)6 was described. Reaction of Fe3 (CO)12 and Me3 SiSCH2 CH2 SSiMe3 in the presence of Et3 N at 80 °C afforded Fe2 (μ‐edt)(CO)6 in 90 % yield. Furthermore, reaction of Fe2 (μ‐edt)(CO)6 and aminodiphosphine ligands (Ph2 P)2 NC6 H4 R (R=−3‐CCH, 4‐CCH) produced the new PNP‐chelated diiron dithiolato complexes Fe2 (μ‐edt)(CO)4 {κ 2 ‐(Ph2 P)2 NC6 H4 R} (1 and 2 ). All the complexes were characterized by elemental analysis, IR, NMR spectroscopy, and particularly for 1 and 2 by X‐ray single diffraction analysis. In addition, the electrochemical results indicated that 1 and 2 could be considered as electrocatalysts for hydrogen evolution reaction. Abstract :