Stepwise Syntheses of Bisporphyrins, Bischlorins, and Biscorroles, and of Porphyrin−Chlorin and Porphyrin−Corrole Heterodimers

Abstract

The stepwise syntheses and characterization of a series of symmetrical and unsymmetrical bisporphyrins, bischlorins, and biscorroles, and of porphyrin−chlorin and porphyrin−corrole dyads possessing ethylene, phenyl, and stilbene linking units are described. The methodology for synthesis of 10-substituted corroles 2 and their cobalt complexes 9 via a, c -biladiene salts 1 was first developed, and then extended to provide biscorroles (e.g., 4 and 5 ) linked through the 10-positions with phenyl linker units. Using a similar methodology, phenyl-linked corrole−porphyrin dyads 28 and 30 were also prepared. By way of intermediate phenyl-linked unsymmetrical bisdipyrromethanes, a completely unsymmetrical heterobimetallic bisporphyrin system, 45, was synthesized. Low-valent titanium coupling (McMurry) reactions were used to prepared stilbene-linked bisdipyrromethanes (e.g., 46 ) which were subsequently transformed into stilbene-linked bisporphyrins (e.g., 48 ). McMurry cross-coupling reactions of porphyrins bearing p -formylphenyl substituents also afforded an unsymmetrically substituted bisporphyrinylstilbene, 60, as well as the corresponding homodimers 56 and 59 . Likewise, McMurry cross-coupling of a p -formylphenyl-substituted porphyrin, 62, with a formylchlorin, 63, afforded a stilbene-linked bisporphyrin, 64, a bischlorin, 66, and a novel porphyrin−chlorin heterodimer, 65 . All novel products were characterized by 1 H NMR, UV−vis, and mass spectroscopy and elemental analysis. X-ray structural information was also obtained for the zinc/nickel bisporphyrin 45 and for the bis-nickel porphyrin−chlorin 65 .