Chemistry related to the [Fe]-Hydrogenases

Abstract : The work in this thesis is focused on the synthesis, reactivity and electrochemistry of chemical models of the active site structures found in [Fe]-hydrogenase, an enzyme that catalyses the reversible reduction of protons to dihydrogen. This enzyme possesses an unusual active site, the “H-cluster”, which is comprised of an {Fe4S4}-cubane linked by a cysteinyl bridge to a di-iron organometallic subsite which is ligated by dithiolate, CO and CN groups.

Chapter I gives a general overview of the biology and chemistry of iron-sulfur proteins and chemical models of their prosthetic groups, with emphasis on the [Fe]-hydrogenase.

Chapter II describes the synthesis, structures and spectroscopic features of 6 new {2Fe3S}-subsite model complexes with a range of functional groups together with X-ray crystallographic structures for all of these.

Chapter III reports and discusses the electrochemical properties of the new {2Fe3S}-complexes. Studies on electrocatalytic hydrogen evolution by these systems are also described.

Chapter IV reports the first synthesis of a free-standing “H-cluster” model complex in which an {Fe4S4}-cubane cluster is coupled to an {2Fe3S}-subsite as in [Fe]-hydrogenase. Spectroscopic, electrochemical and DFT calculations provide an insight into the electronic properties of the synthetic assembly and this is placed in the context of the natural system.

Chapter V describes some early results on the incorporation of synthetic di-iron subsites into electropolymers to provide solid-state electrocatalysts together with the prospects for future work in the area.
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Cédric Tard. Chemistry related to the [Fe]-Hydrogenases. Other. University of East Anglia, Norwich, 2005. English. ⟨tel-00011568⟩

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