Synthesis of rare-earth-metal-in-cryptand dications, [Ln(2.2.2-cryptand)]2+, from Sm2+, Eu2+, and Yb2+ silyl metallocenes (C5H4SiMe3)2Ln(THF)2

Daniel N Huh; Christopher M Kotyk; Milan Gembicky; Arnold L Rheingold; Joseph W Ziller; William J Evans

doi:10.1039/c7cc04396a

Synthesis of rare-earth-metal-in-cryptand dications, [Ln(2.2.2-cryptand)]²⁺, from Sm²⁺, Eu²⁺, and Yb²⁺ silyl metallocenes (C₅H₄SiMe₃)₂Ln(THF)₂

Chem Commun (Camb). 2017 Aug 11;53(62):8664-8666. doi: 10.1039/c7cc04396a. Epub 2017 Jul 19.

Authors

Daniel N Huh¹, Christopher M Kotyk¹, Milan Gembicky², Arnold L Rheingold², Joseph W Ziller¹, William J Evans¹

Affiliations

¹ Department of Chemistry, University of California-Irvine, Irvine, California 92697, USA. wevans@uci.edu.
² Department of Chemistry and Biochemistry, University of California-San Diego, La Jolla, California 92093, USA.

PMID: 28722066
DOI: 10.1039/c7cc04396a

Abstract

Cp'₂Ln(THF)₂ metallocenes (Cp' = C₅H₄SiMe₃) react with 2.2.2-cryptand (crypt) to form Ln²⁺-in-crypt complexes, [Ln(crypt)(THF)][Cp'₃Ln]₂ (Ln = Sm, Eu) and [Yb(crypt)][Cp'₃Yb]₂, that contain Ln²⁺ ions surrounded only by neutral ligands. A bimetallic, mixed-ligand metallocene/opened-crypt complex of Sm²⁺, [Sm(C₁₆H₃₂N₂O₆-κ²O:κ²O')SmCp''₂], was obtained by KC₈ reduction of Cp''₂Sm(THF) [Cp'' = C₅H₃(SiMe₃)₂] in the presence of crypt.