Binuclear organometallic ruthenium complexes of a Schiff base expanded porphyrin

摘要

The synthesis of binuclear organometallic ruthenium complexes of an expanded porphyrin-type macrocycle is reported; pyrrolic hydrogen bonding donors were found to interact with ancillary ligands in the primary coordination sphere and to stabilize coordinated dioxygen in an η~2-fashion.rnCore-expanded porphyrin analogs constitute a diverse class of macrocyclic ligands that display a range of cavity geometries and sizes, optical properties and coordinative functionalities. Owing to their similarity to natural tetrapyrroles, expanded porphyrins have attracted considerable interest as platforms for the preparation of new metal complexes, as well as the exploration of reactivity patterns that have no known parallel in the case of natural porphyrins. For instance, Schiff-base expanded porphyrin macrocycles have been used to stabilize non-labile 1 : 1 lanthanide complexes, to provide molecular frameworks for the cooperative action of two metals onto one substrate, including positive allosteric binding processes, and, recently, to illustrate an unprecedented reactivity pattern for the uranyl cation.