Alkyl and aryl substituted corroles. 2. Synthesis and characterization of linked 'face-to-face' biscorroles. X-ray structure of (BCA)Co-2(py)(3), where BCA represents a biscorrole with an anthracenyl bridge

摘要

The synthesis, spectroscopic properties, and electrochemistry of (BCA)CO2 and (BCB)CO2 are described where BCA and BCB represent biscorroles linked by an anthracenyl (A) or a biphenylenyl (B) bridge. The pyridine and CO binding properties of (BCA)Co-2 and (BCB)Co-2 are also presented, and one of the compounds in its pyridine-ligated form, (BCA)Co-2(py)(3), is structurally characterized. The data on the biscorroles arc compared on one hand to the monocorrole having the same substitution pattern and on the other hand to bisporphyrins having two Co(II) ions and the same anthracenyl or biphenylenyl linkers in order to better understand the interaction which occurs between the two corrole macrocycles. A parallel study on five different Co(III) phenyl-substituted corroles showed that bis-pyridine and mono-CO adducts are readily formed from the complexes in CH2Cl2. This present paper examines how the ligand binding properties and electrochemistry of these Co(III) corroles are modified by the anthracenyl or biphenylenyl bridge which links the two macrocycles in a face to face orientation. An X-ray crystal structure was obtained for the tris-pyridine adduct of the anthracenyl bridged derivative, (BCA)Co-2(py)(3), and gives the following results: C127H99Co2N11. 2CHCl(3), M = 2135.90, triclinic, space group P (1) over bar, a = 13.2555(5) Angstrom, b = 18.6406(8) Angstrom, c = 22.2140(9) Angstrom, alpha = 94.186(9)degrees, beta = 102.273(9)degrees, gamma = 94.205(9)degrees, V = 5326.8(4) Angstrom (3), 9293 independent reflections collected, R(F) = 0.066. [References: 79]