Synthesis, structure and properties of ferrocene functionalized porphyrins

Abstract

A series of free-base and metallated mixed ferrocenamido- and pivalamidophenylporphyrins have been prepared from the α,α’,α’’,α’’’ isomer of 5,10,15,20-tetra(o-aminophenyl)porphyrin. The X-ray crystal structure of the iron(III) α,α’,α’’,α’’’-5,10,15,20-tetrakis(o-ferrocenamidophenyl)- porphyrin bromide has been determined and compared with related structures of cobalt(III) α,α’,α’’,α’’’- 5,10,15,20-tetrakis(o-pivalamidophenyl)porphyrin bromide pyridine and the free base α,α’,α’’,α’’’- 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.