Synthesis of LnII-in-Cryptand Complexes by Chemical Reduction of LnIII-in-Cryptand Precursors: Isolation of a NdII-in-Cryptand Complex |
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| Authors: | Daniel N Huh Sierra R Ciccone Samuel Bekoe Saswata Roy Joseph W Ziller Prof Filipp Furche Prof William J Evans |
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| Institution: | Department of Chemistry, University of California, Irvine, Irvine, CA, 92697 USA |
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| Abstract: | Lanthanide triflates have been used to incorporate NdIII and SmIII ions into the 2.2.2-cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf)3 complexes (Ln=Nd, Sm; OTf=SO3CF3) react with crypt in THF to form the THF-soluble complexes LnIII(crypt)(OTf)2]OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these LnIII-in-crypt complexes using KC8 in THF forms the neutral LnII-in-crypt triflate complexes LnII(crypt)(OTf)2]. DFT calculations on NdII(crypt)]2+], the first NdII cryptand complex, assign a 4f4 electron configuration to this ion. |
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| Keywords: | coordination chemistry cryptand complexes electrochemistry lanthanides reduction |
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