Issue 21, 2003

Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships

Abstract

A series of binuclear FeIFeI complexes, (μ-SEt)2[Fe(CO)2L]2 (L = CO (1), PMe3 (1-P)), (μ-SRS)[Fe(CO)2L]2 (R = CH2CH2 (μ-edt): L = CO (2), PMe3 (2-P); R = CH2CH2CH2(μ-pdt): L = CO (3), PMe3 (3-P); and R = o-CH2C6H4CH2 (μ-o-xyldt): L = CO (4), PMe3 (4-P)), that serve as structural models for the active site of Fe-hydrogenase are shown to be electrocatalysts for H2 production in the presence of acetic acid in acetonitrile. The redox levels for H2 production were established by spectroelectrochemistry to be Fe0Fe0 for the all-CO complexes and FeIFe0 for the PMe3-substituted derivatives. As electrocatalysts, the PMe3 derivatives are more stable and more sensitive to acid concentration than the all-CO complexes. The electrocatalysis is initiated by electrochemical reduction of these diiron complexes, which subsequently, under weak acid conditions, undergo protonation of the reduced iron center to produce H2. An (η2-H2)FeII–Fe0/I intermediate is suggested and probable electrochemical mechanisms are discussed.

Graphical abstract: Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships

Supplementary files

Article information

Article type
Paper
Submitted
17 Dzi 2003
Accepted
30 Mud 2003
First published
22 Ndz 2003

Dalton Trans., 2003, 4158-4163

Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships

D. Chong, I. P. Georgakaki, R. Mejia-Rodriguez, J. Sanabria-Chinchilla, M. P. Soriaga and M. Y. Darensbourg, Dalton Trans., 2003, 4158 DOI: 10.1039/B304283A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements