Structural Determination of an Unusual Cu(I)‐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.