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[FeFe]-Hydrogenase synthetic mimics based on peri-substituted dichalcogenides

Figliola, Carlotta (2015)
Ph.D. thesis, University of Birmingham.

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[FeFe]-hydrogenase plays an important role in the microbial energy metabolism, catalysing the reduction of protons into molecular hydrogen. Herein the synthesis and the spectroscopic analysis (NMR, IR, UV/vis) of [FeFe]-complexes based on the naphtho[1,8-cd][1,2]dithiole, naphtho[1,8-cd][1,2]diselenole and naphtho[1,8-cd][1,2]thiaselenole backbone, which incorporate substituents in position 2 of the naphthalene ring (OMe, tBu) are described. Additionally, dichalcogenide-based [FeFe]-complexes, containing the rigid aromatic phenanthrene and fluorene backbones are discussed. Cyclic voltammetry was applied in order to investigate the electrochemical properties of these new [FeFe]-hydrogenase synthetic analogues. Titration with pTsOH was monitored by cyclic voltammetry and showed that these [FeFe]-complexes are catalysts for proton reduction. After having studied these promising systems for proton reduction catalysis, the functionalization of naphthalene-1,8-dithiolate and diselenolate-based [FeFe]-complexes by insertion of aromatic and alkyl amino and imino groups is described. Spectroscopic and electrochemical techniques were applied to confirm protonation of the nitrogen, upon acid addition, and the effect on proton reduction catalysis, which was remarkably improved. Following these results, the synthesis of a molecular dyad containing zinc tetraphenylporphyrin, covalently linked to naphthalene-1,8-dithiolate-based [FeFe]-complex, via amino group, is reported. The initial investigations (UV/vis and emission spectroscopy) showed catalytic photo-induced hydrogen production, which was monitored by gas chromatography.

Type of Work:Ph.D. thesis.
Supervisor(s):Grainger, Richard S.
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:5540
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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