Structural Determination of an Unusual CuI -Porphyrin-π-Bond in a Hetero-Pacman Cu-Zn-Complex.

The synthesis and characterization of a hetero-dinuclear compound is presented, in which a copper(I) trishistidine type coordination unit is positioned directly above a zinc porphyrin unit. The close distance between the two coordination fragments is secured by a rigid xanthene backbone, and a unique (intramolecular) copper porphyrin-π-bond was determined for the first time in the molecular structure. This structural motif was further analyzed by temperature-dependent NMR studies: In solution at room temperature the coordinative bond fluctuates, while it can be frozen at low temperatures. Preliminary reactivity studies revealed a reduced reactivity of the copper(I) moiety towards dioxygen. The results adumbrate why nature is avoiding metal porphyrin-π-bonds by fixing reactive metal centers in a predetermined distance to each other within multimetallic enzymatic reaction centers.