Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization

Article abstract of DOI:10.1021/ic0501622

The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Ch anion on the cobalt corrole. Structural data: (PCB)FeClCoCl·0.5(C ₇H₁₆)·0.5(CH₂Cl₂) ·2H₂O, triclinic, space group P1^-, a = 13.8463(3) A, b = 16.8164(5) A, c = 17.9072(6) A, α = 93.780(1)°, β= 111.143(1)°, γ = 97.463(2)°, Z=2.