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

Citations Over TimeTop 10% of 1996 papers

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 1H 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.

Related Papers

• → Porphyrins in 1,3-Dipolar Cycloaddition Reactions. Synthesis of New Porphyrin−Chlorin and Porphyrin−Tetraazachlorin Dyads(2006)56 cited
• → Room‐Temperature Autoconversion of Free‐Base Corrole into Free‐Base Porphyrin(2006)51 cited
• → Porphyrin derivatives: Synthesis and potential applications(2000)22 cited
• → Structural and Electronic Properties of Co-corrole, Co-corrin, and Co-porphyrin(2000)92 cited
• → Synthesis and Properties of Metal Complexes of Ether-bonded Porphyrin–Chlorin Dimer(1994)2 cited