title: Acid-base and spectroelectrochemical properties of doubly N-confused porphyrins.
abstract: The cis-doubly N-confused porphyrin, H2N2CP, containing two adjacent confused pyrrole rings has been investigated from the point of view of its acid-base and electrochemical behavior in dichloromethane. This novel porphyrin isomer can form two metal-carbon bonds in the central core, stabilizing metal ions in unusually high oxidation states. Furthermore, the two outside N-pyrrole atoms remain available for acid-base and specific solvent interactions. Protonation of the pyrrole N atoms proceeds according to two successive steps, while only a single deprotonation step has been observed in the presence of bases. Similarly, in the case of the silver and copper complexes the protonation and deprotonation of the outer pyrrole rings have been detected, confirming the structure of the metalated species as M(III)-HN2CP. The electrochemical reduction of the metal ions (III/II redox process) and oxidation of the macrocycle ring have been detected respectively at -0.9 and 1.4 V based on spectroelectrochemical measurements in conjunction with the acid/base equilibrium studies. Additional waves observed around -0.5 and 1.3 V have been assigned to redox processes involving water molecules associated with the doubly N-confused porphyrins.
authors: Instituto de Química, Universidade de São Paulo, C. Postal 26077, CEP 05513-970, São Paulo (SP), Brazil. koiaraki@iq.usp.br
authors: K
authors: K
authors: Araki
authors: H
authors: H
authors: Winnischofer
authors: H E
authors: HE
authors: Toma
authors: H
authors: H
authors: Maeda
authors: A
authors: A
authors: Osuka
authors: H
authors: H
authors: Furuta