Copper(II) and Copper(III) Complexes of Pyrrole-Appended Oxacarbaporphyrin

The reaction of an O-confused porphyrin with a pendant pyrrole 4 and copper(II) acetate yields an organocopper(III) diamagnetic complex 4-Cu(III) substituted at the C(3) position by the pyrrole and H. The transformation of
4-Cu(III), performed in aerobic conditions, gave a rare copper(II) organometallic compound 6-Cu(II). In the course
of this process, the tetrahedral−trigonal rearrangement originated at the C(3) atom but effects the whole structure.
The electron paramagnetic resonance spectroscopic features correspond to a copper(II) oxidation state. A
crystallographic analysis of 6-Cu(II) confirmed the formation of a direct metal−C bond [Cu(II)−C 1.939(4) Å]. It was
found that the Cu(II) complex of O-confused oxaporphyrin is sensitive to oxidative conditions. The degradation of
6-Cu(II) to yield copper(II) tripyrrinone complexes has been observed, which was considered as a peculiar case of
dioxygen activation in a porphyrin-like environment. This process is accompanied by regioselective oxygenation at
the inner C to form the 2-oxa-3-(2‘-pyrrolyl)-21-hydroxycarbaporphyrinatocopper(II) complex ((pyrr)OCPO)CuII (8).
The reaction of 6-Cu(II) with hydrogen peroxide, performed under heterophasic conditions, resulted in quantitative
regioselective hydroxylation centered at the internal C(21) atom, also producing 8. Treatment of 8 with acid results
in demetalation to form the nonaromatic 21-hydroxy O-confused porphyrin derivative ((pyrr)OCPOH)H (9).