Nickel (II) pyrrocorphin: Enhanced binding ability in a highly reduced porphyrin complex

Pyrrocorphin is an air-sensitive porphyrinoid with a highly reduced hexahydroporphyrin core. In contrast, pyrrolidine-fused pyrrocorphin (Pyr) obtained by successive 1,3-dipolar cycloaddition reactions of azomethine ylide to 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin is less air-sensitive. In order to reveal the effect of highly reduced porphyrin rings on the physicochemical properties of their metal complexes, we have prepared diamagnetic (S=0) Ni(II) complex Ni(II)(Pyr). The addition of excess pyridine (Py) to the toluene solution of Ni(II)(Pyr) yielded five-coordinate Ni(II)(Pyr)(Py), which was then completely converted to six-coordinate paramagnetic (S=1) Ni(II)(Pyr)(Py)₂. The latter was characterized by UV-Vis, ¹H NMR, CV, SQUID, and X-ray crystallography as well as DFT calculations. As compared with analogous complexes of porphyrin (Por), chlorin (Chl), and isobacteriochlorin (Iso) reported by Herges and co-workers (R. Herges et al., Inorg. Chem. 2015), Ni(II)(Pyr)(Py)₂ has longer equatorial NiN and shorter axial NiN bonds. The CV study has shown a large decrease in HOMO-LUMO gap as the reduction of porphyrin ring proceeds, which has further been confirmed by UV-Vis and DFT calculation. Titration studies using ¹H NMR and UV-Vis have shown that the first binding constant of pyridine toward Ni(II)(Pyr) is ca. 4 times as large as that of Ni(II)(Iso) and ca 230 times as large as that of Ni(II)(Por). Thus, we have concluded that the binding constant of pyridine to Ni(II) porphyrinoid increases by the following order: Por