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 H2 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 H2. 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 H2 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 −NO2 substituent results in faster H2 oxidation relative to that of a −OCH3 substituent.

Abhijit Nayek

Rabin Kumar Poria

Md Estak Ahmed

Suman Patra

Somdatta Ghosh Dey

Abhishek Dey

ACS Organic & Inorganic Au

ACS Organic and Inorganic Au

Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase

受仿生模型[FeFe]-氢化酶催化的氢氧化

Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase

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Journal Info

Category	Quartile
CHEMISTRY, MULTIDISCIPLINARY	2