Synthesis of Ln -in-Cryptand Complexes by Chemical Reduction of Ln -in-Cryptand Precursors: Isolation of a Nd -in-Cryptand Complex

Lanthanide triflates have been used to incorporate Nd and Sm ions into the 2.2.2-cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf) complexes (Ln=Nd, Sm; OTf=SO CF ) react with crypt in THF to form the THF-soluble complexes [Ln (crypt)(OTf) ][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these Ln -in-crypt complexes using KC in THF forms the neutral Ln -in-crypt triflate complexes [Ln (crypt)(OTf) ]. DFT calculations on [Nd (crypt)] ], the first Nd cryptand complex, assign a 4f electron configuration to this ion.