Porphodimethene−Zirconium: A New Entry into Zirconium Macrocycle Organometallic Chemistry

The cis-dichloro-meso-hexaethylporphodimethene−zirconium(IV) complex has been functionalized
to the corresponding dialkyl derivatives [R = Me, PhCH2,
Ph], 3−5, displaying a variety of migratory pathways.
In the case of benzyl derivative 4, the spontaneous
migration of the first benzyl to the ligand, 6, is followed
by the second one, photochemically induced, thus forming a Zr−porphyrinogen complex, 7. The methyl derivative undergoes thermally induced methane elimination
with the metalation of the meso ethyl chains, 8. Migration of both methyl groups has been observed in the
reaction of 3 with ButNC, with the preliminary formation of η2-imine, rearranging to the corresponding enamine, 9.