Redox active iron nitrosyl units in proton reduction electrocatalysis

Chung-Hung Hsieh, Shengda Ding, Özlen F. Erdem, Danielle J. Crouthers, Tianbiao Liu, Charles C. L. McCrory, Wolfgang Lubitz, Codrina V. Popescu, Joseph H. Reibenspies, Michael B. Hall and Marcetta Y. Darensbourg ()
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Chung-Hung Hsieh: Texas A&M University
Shengda Ding: Texas A&M University
Özlen F. Erdem: Max Planck Institute for Chemical Energy Conversion
Danielle J. Crouthers: Texas A&M University
Tianbiao Liu: Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory
Charles C. L. McCrory: Joint Center for Artificial Photosynthesis, California Institute of Technology
Wolfgang Lubitz: Max Planck Institute for Chemical Energy Conversion
Codrina V. Popescu: Ursinus College
Joseph H. Reibenspies: Texas A&M University
Michael B. Hall: Texas A&M University
Marcetta Y. Darensbourg: Texas A&M University

Nature Communications, 2014, vol. 5, issue 1, 1-8

Abstract: Abstract 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.

Date: 2014
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DOI: 10.1038/ncomms4684

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