Synthesis and characterization of the most distorted 16π porphyrin: 16π octaisopropyltetraphenylporphyrin (OiPTPP)

Abstract

Previously unreported octaisopropyltetraphenylporphyrin (OiPTPP) was prepared from 3,4-diisopropylpyrrole, an unstable previously unisolated heterocyclic compound. Purification of the free-base 18π porphyrin required conversion to its 18π zinc(II) complex, chromatographic separation, and acid mediated demetalation. Oxidation of the 18π porphyrin with SbCl5 furnished metal-free 16π octaisopropyltetraphenylporphyrin (OiPTPP). X-ray structural determination revealed that the novel species is the most distorted 16π porphyrin to date. The time course of decomposition of the oxidized species monitored by UV-vis spectra implied that the introduction of high steric repulsion was effective for enhancing stability of the 16π porphyrin. The reaction of metal-free 16π OiPTPP with LiBF4 followed by Pd2(dba)3 gave the corresponding 18π OiPTPP palladium(II) complex via reduction of the OiPTPP lithium(I) complex as previously reported for 16π octaisobutyltetraphenylporphyrin (OiBTPP). The new 18π porphyrin system could be characterized by the X-ray analysis of the 18π OiPTPP palladium(II) complex. The X-ray structure of the 18π metal complex also indicated that the distortion of the porphyrin ring had become larger than that of previously known 18π porphyrins