New example of hemiporphycene formation from the corrole ring expansion.

Research paper by Yuanyuan Y Fang, Federica F Mandoj, Sara S Nardis, Giuseppe G Pomarico, Manuela M Stefanelli, Daniel O DO Cicero, Sara S Lentini, Andrea A Vecchi, Yan Y Cui, Lihan L Zeng, Karl M KM Kadish, Roberto R Paolesse

Indexed on: 01 Jul '14Published on: 01 Jul '14Published in: Inorganic Chemistry


The reaction of 5,10,15-tris(4-tert-butylphenyl)corrole with 2,3-bis(bromomethyl)-5,6-dicyanopyrazine provides a new example of corrole ring expansion to a hemiporphycene derivative. The ring expansion is regioselective, with insertion of the pyrazine derivative at the 5-position of the corrole ring, affording the corresponding 5-hemiporphycene. Different macrocyclic products accompany formation of the 5-hemiporphycene, depending on the reaction experimental conditions. Br-substitued 5-hemiporphycenes and the 2-Br substituted corrole were obtained in 1,2,4-trichlorobenzene, while in refluxing toluene traces of an inner core substituted corrole were observed together with a significant amount of the unreacted corrole. These results provide an important indication of the reaction pathway. The coordination behavior of the 5-hemiporphycene, together with detailed electrochemical characterization of the free-base and some metal complexes, provides evidence for the reactivity of the peripheral pyrazino group.