Demetalation of metallocorroles

Abstract

Although the chemistry of corroles has grown spectacularly in recent years, the field has been marred by the lack of convenient protocols for demetalation of metallocorroles. In this thesis, I have developed a superior procedure for demetalating copper corroles with concentrated H2SO4 and 5-200 equiv FeCl2 or SnCl2. The yields obtained with this reductive procedure are generally substantially better than with HCl3/H2SO4, CH2Cl2/H2SO4, or H2SO4 alone. With an oxidation-prone metallocorrole such as Cu[T(p-OMeP)C], the reductive protocol was essential for obtaining any measurable yield of the free base at all. Free-base β-octabromo-mesotriarylcorroles were also obtained in pure form, in good yields, and with relative ease via this procedure.