PHOTOCATALYSIS, PHOTOREDUCTION, PHOTOOXIDATION AND PHOTOREDOX HYDROGEN TRANSFER REACTIONS OF METALLOPORPHYRINS

Abstract

Abstract— Hydrogen transfer from tertiary amines to nitroaromatics is photocatalysed by SnIV and GeIV complexes of tetraphenylporphyrin. There are two photochemical steps, one involving hydrogen transfer to the catalyst, and the second being a hydrogen donation from the intermediate formed. The photoredox properties of para‐substituted tin tetraphenyl porphyrin dichlorides can be correlated with the one electron oxidation‐reduction potentials of the porphyrins and of the reduced intermediates. The steady‐state concentration of intermediate and rate of product formation depend also on the electron donor and acceptor properties of, respectively, the amine and nitro‐compound. Fluorescence results indicate that in both photochemical steps excited singlet states of porphyrins are involved and there is evidence for exciplex formation with ground state amine. Acetic anhydride has a cocatalytic effect but does not influence the quenching of porphyrin fluorescence by amine or the quertchirjg of the fluorescence of the intermediate by nitrobenzene.