Redox active iron nitrosyl units in proton reduction electrocatalysis

Base metal, molecular catalysts for the fundamental process of conversion of protons and electrons to dihydrogen, remain a substantial synthetic goal related to a sustainable energy future. Here we report a diiron complex with bridging thiolates in the butterfly shape of the 2Fe2S core of the [FeFe]...

Full description

Saved in:
Bibliographic Details
Published in:Nature communications 2014-05, Vol.5 (1), p.3684-3684, Article 3684
Main Authors: Hsieh, Chung-Hung, Ding, Shengda, Erdem, Özlen F, Crouthers, Danielle J, Liu, Tianbiao, McCrory, Charles C L, Lubitz, Wolfgang, Popescu, Codrina V, Reibenspies, Joseph H, Hall, Michael B, Darensbourg, Marcetta Y
Format: Article
Language:English
Subjects:
Catalysis
Electrochemical Techniques
Electron Spin Resonance Spectroscopy
Iron - chemistry
Nitrogen Oxides - chemistry
Oxidation-Reduction
Protons
Spectroscopy, Mossbauer
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Base metal, molecular catalysts for the fundamental process of conversion of protons and electrons to dihydrogen, remain a substantial synthetic goal related to a sustainable energy future. Here we report a diiron complex with bridging thiolates in the butterfly shape of the 2Fe2S core of the [FeFe]-hydrogenase active site but with nitrosyl rather than carbonyl or cyanide ligands. This binuclear [(NO)Fe(N2S2)Fe(NO)2](+) complex maintains structural integrity in two redox levels; it consists of a (N2S2)Fe(NO) complex (N2S2=N,N'-bis(2-mercaptoethyl)-1,4-diazacycloheptane) that serves as redox active metallodithiolato bidentate ligand to a redox active dinitrosyl iron unit, Fe(NO)2. Experimental and theoretical methods demonstrate the accommodation of redox levels in both components of the complex, each involving electronically versatile nitrosyl ligands. An interplay of orbital mixing between the Fe(NO) and Fe(NO)2 sites and within the iron nitrosyl bonds in each moiety is revealed, accounting for the interactions that facilitate electron uptake, storage and proton reduction.
ISSN:2041-1723
2041-1723
DOI:10.1038/ncomms4684