N-Derivatives of peri-Substituted Dichalcogenide [FeFe]-Hydrogenase Mimics: Towards Photocatalytic Dyads for Hydrogen Production

Synthetic strategies towards molecular dyads based on peri‐substituted dichalcogenide (S,Se) [FeFe]‐hydrogenase synthetic mimics covalently linked to a ZnTPP photosensitizer are described. Dithiolate and diselenolate model systems 2–5 are prepared through condensation of 2‐naphthaldehydes with p‐met...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2015-07, Vol.2015 (19), p.3146-3156
Main Authors: Figliola, Carlotta, Male, Louise, Horswell, Sarah L., Grainger, Richard S.
Format: Article
Language:English
Subjects:
Amines
Bonding
Carbonyl ligands
Catalysis
Chemical Sciences
Coordination chemistry
Covalence
Cyclic voltammetry
Electrocatalysis
Imines
Insertion
Mathematical models
Photocatalysis
Porphyrinoids
Reduction
Zinc
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Summary:Synthetic strategies towards molecular dyads based on peri‐substituted dichalcogenide (S,Se) [FeFe]‐hydrogenase synthetic mimics covalently linked to a ZnTPP photosensitizer are described. Dithiolate and diselenolate model systems 2–5 are prepared through condensation of 2‐naphthaldehydes with p‐methoxyaniline, reduction of the resulting Schiff base and oxidative insertion of Fe2(CO)6 into the dichalcogen bond of the imine or amine. Diselenolate‐based [FeFe] complexes (imine 3 and amine 5) are more efficient in electrocatalysis of proton reduction than their sulfur analogues 2 and 4 with increasing concentrations of pTsOH. Molecular dyad 1 containing a peri‐substituted naphthalene dithiolate Fe2(CO)6 cluster covalently linked via an amine to ZnTPP is prepared through sequential zinc insertion into the porphyrin followed by iron insertion into the disulfide bond. peri‐Substituted naphthalenedithiolate and diselenolate‐based mimics of [FeFe]‐hydrogenase, appended at the 2‐position with basic amine and imine functionalities, are electrocatalysts for the conversion of protons to diatomic hydrogen. The synthesis of a molecular dyad, consisting of a zinc tetraphenylporphyrin photosensitizer covalently linked via an amine in close proximity to the catalytically active site, is also reported.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201500355