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-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. [ABSTRACT FROM AUTHOR]