Porphyrinatonickel(II)-Cyclopentene and Porphyrinatonickel(II)-Cyclopentadiene Hybrids: Zirconacyclopentadiene-Mediated Syntheses, Structures, and Mechanistic Study

The reaction of meso-formyl Ni(II) porphyrin 1 with zirconacyclopentadiene 2 in the presence of AlCl3 afforded four products 3, 4, 5, and 6 with a total yield of over 85%. The structures of these compounds are well-characterized by H-1 NMR an d13C NMR spectroscopy, HRMS, and X-ray single-crystal diffraction. The mechanism is proposed mainly on the basis of isotopic labeling experiments, which showed that a Friedel-Crafts-type reaction and beta-H shift may be critical during the formation of 5 and 6.

Automated summary

In the presence of AlCl3, the reaction between meso-formyl Ni(II) porphyrin 1 and zirconacyclopentadiene 2 yielded four products 3, 4, 5, and 6 with a total yield of over 85%. The structures of these compounds were well-characterized, and the mechanism of their formation was proposed based on isotopic labeling experiments, suggesting the involvement of a Friedel-Crafts-type reaction and beta-H shift.