Heterobimetallic Complexes of Cobalt(IV) Porphyrin−Corrole Dyads. Synthesis, Physicochemical Properties, and X-ray Structural Characterization

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
Cl- anion on the cobalt corrole. Structural data:  (PCB)FeClCoCl·0.5(C7H16)·0.5(CH2Cl2)·2H2O, triclinic, space group
P1̄, a = 13.8463(3) Å, b = 16.8164(5) Å, c = 17.9072(6) Å, α = 93.780(1)°, β = 111.143(1)°, γ = 97.463(2)°,
Z = 2.