Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase
Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Synthetic azadithiolate-bridged diiron clusters serve as structural analogues of the active site of [FeFe]-hydrogenases. Recently, an o- alkyl substitution of aniline-based azadithiolate bridge allowed these synthetic models to both oxidize H 2 and reduce H +, i.e., bidirectional catalysis. Hydrogen oxidation by synthetic analogues of hydrogenases is rare, and even rarer is the ability of diiron hexacarbonyls to oxidize H 2 . A series of synthetic azadithiolate-bridged biomimetic diiron hexacarbonyl complexes are synthesized where the substitution in the para position of the ortho- methyl aniline in the azadithiolate bridge is systematically varied between electron-withdrawing and electron-donating groups to understand factors that control H 2 oxidation by diiron hexacarbonyl analogues of [FeFe]-hydrogenases. The results show that the substituents in the para position of the ortho- ethyl aniline affect the electronic structure of the azadithiolate bridge as well as that of the diiron cluster. The electron-withdrawing −NO 2 substituent results in faster H 2 oxidation relative to that of a −OCH 3 substituent.
Source: ACS Organic & Inorganic Au
Institution: Indian Association for the Cultivation of Science
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,500
Award: G532924003
OpenAlex ID: W4404958503