The Synthesis of a Corrole Analogue of Aquacobalamin (Vitamin B_12a) and Its Ligand Substitution Reactions

The synthesis of a Co­(III) corrole, [10-(2-[[4-(1H-imidazol-1-ylmethyl)­benzoyl]­amino]­phenyl)-5,15-diphenylcorrolato]­cobalt­(III), DPTC-Co, bearing a tail motif terminating in an imidazole ligand that coordinates Co­(III), is described. The corrole therefore places Co­(III) in a similar environment to that in aquacobalamin (vitamin B_12a, H₂OCbl⁺) but with a different equatorial ligand. In coordinating solvents, DPTC-Co is a mixture of five- and six-coordinate species, with a solvent molecule occupying the axial coordination site trans to the proximal imidazole ligand. In an 80:20 MeOH/H₂O solution, allowed to age for about 1 h, the predominant species is the six-coordinate aqua species [H₂O–DPTC-Co]. It is monomeric at least up to concentrations of 60 μM. The coordinated H₂O has a pK_a = 9.76(6). Under the same conditions H₂OCbl⁺ has a pK_a = 7.40(2). Equilibrium constants for the substitution of coordinated H₂O by exogenous ligands are reported as log K values for neutral N-, P-, and S-donor ligands, and CN^–, NO₂^–, N₃^–, SCN^–, I^–, and Cys in 80:20 MeOH/H₂O solution at low ionic strength. The log K values for [H₂O–DPTC-Co] correlate reasonably well with those for H₂OCbl⁺; therefore, Co­(III) displays a similar behavior toward these ligands irrespective of whether the equatorial ligand is a corrole or a corrin. Pyridine is an exception; it is poorly coordinated by H₂OCbl⁺ because of the sterically hindered coordination site of the corrin. With few exceptions, [H₂O–DPTC-Co] has a higher affinity for neutral ligands than H₂OCbl⁺, but the converse is true for anionic ligands. Density functional theory (DFT) models (BP86/TZVP) show that the Co–ligand bonds tend to be longer in corrin than in corrole complexes, explaining the higher affinity of the latter for neutral ligands. It is argued that the residual charge at the metal center (+2 in corrin, 0 in corrole) increases the affinity of H₂OCbl⁺ for anionic ligands through an electrostatic attraction. The topological properties of the electron density in the DFT-modeled compounds are used to explore the nature of the bonding between the metal and the ligands.