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) A]. 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).