Synthesis of Ln<sup>II</sup>‐in‐Cryptand Complexes by Chemical Reduction of Ln<sup>III</sup>‐in‐Cryptand Precursors: Isolation of a Nd<sup>II</sup>‐in‐Cryptand Complex
Daniel N. Huh, Sierra R. Ciccone, Samuel Bekoe, Saswata Roy, Joseph W. Ziller, Filipp Furche, William J. Evans
Abstract
Abstract Lanthanide triflates have been used to incorporate Nd III and Sm III ions into the 2.2.2‐cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf) 3 complexes (Ln=Nd, Sm; OTf=SO 3 CF 3 ) react with crypt in THF to form the THF‐soluble complexes [Ln III (crypt)(OTf) 2 ][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these Ln III ‐in‐crypt complexes using KC 8 in THF forms the neutral Ln II ‐in‐crypt triflate complexes [Ln II (crypt)(OTf) 2 ]. DFT calculations on [Nd II (crypt)] 2+ ], the first Nd II cryptand complex, assign a 4f 4 electron configuration to this ion.
Topics & Concepts
CryptandCryptChemistryTrifluoromethanesulfonateLanthanideLigand (biochemistry)MetalIonMedicinal chemistryCrystallographyStereochemistryInorganic chemistryOrganic chemistryCatalysisReceptorBiochemistryEndocrinologyMedicineSupramolecular Chemistry and ComplexesLanthanide and Transition Metal ComplexesRadioactive element chemistry and processing