A Highly Reactive Uranium Complex Supported by the Calix[4]tetrapyrrole Tetraanion Affording Dinitrogen Cleavage, Solvent Deoxygenation, and Polysilanol Depolymerization

The importance of atmosphere: The reaction of [(Et8-calix[4]tetrapyrrole)U(dme)][K(dme)] and [K(naphthalenide)] yields remarkable dimeric complexes, the structures of which are dependent on the atmospheric gases employed. Reaction under N2 leads to dinitrogen cleavage and a μ-KN bridged dimer (see picture). In contrast, reactions performed in an Ar atmosphere promoted solvent deoxygenation, as well as reaction with silicon grease. dme=1,2-Dimethoxyethane.