Synthesis, structure and properties of ferrocene functionalized porphyrins

A series of free-base and metallated mixed ferrocenamido- and pivalamidophenylporphyrins have been prepared from the alpha,alpha',alphaalpha",alpha''' isomer of 5,10,15,20-tetra(o-aminophenyl)porphyrin. The X-ray crystal structure of the iron(III) alpha,alpha',alpha",alpha"'-5,10,15,20-tetrakis(o-ferrocenamidophenyl)porphyrin bromide has been determined and compared. with related structures of cobalt(III) alpha,alpha',alpha",alpha'''-5,10,15,20-tetrakis(o-pivalamidophenyl)porphyrin bromide pyridine and the free base alpha,alpha',alpha",alpha'''-5,10,15,20-tetrakis(o-pivalamidophenyl)porphyrin. In both metalloporphyrins the coordinated axial bromides are contained in the cavity formed by the appended pickets with all the amide N-H bonds directed toward the anion. Copyright (C) 2002 Society of Porphyrins & Phthalocyanines.