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Lewis‐Acid Stabilized Organoimide Complexes of Divalent Samarium, Europium, and Ytterbium
Author(s) -
Wolf Benjamin M.,
Stuhl Christoph,
MaichleMössmer Cäcilia,
Anwander Reiner
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803619
Subject(s) - chemistry , samarium , europium , protonolysis , ionic radius , metathesis , ytterbium , divalent , steric effects , medicinal chemistry , inorganic chemistry , lewis acids and bases , crystallography , stereochemistry , catalysis , organic chemistry , polymerization , polymer , ion , materials science , optoelectronics , doping
Discrete organoimide complexes of the divalent rare‐earth metals samarium, europium, and ytterbium are reported. Tandem salt metathesis‐protonolysis reactions using Ln II bis(tetramethylaluminate) precursors [Ln(AlMe 4 ) 2 ] n and monopotassium salts of 2,6‐diisopropylaniline (H 2 NDipp) and triphenylsilylamine prove viable and efficient protocols. Depending on the ionic radius of the Ln II metal centers and the steric demand of the imido carbon backbone, mono‐ and dilanthanide arrangements of general composition [(thf) x Ln(NR)(AlMe 3 )] y (Ln=Sm, Eu, Yb; R=Dipp, SiPh 3 ) are found in the solid state. Complex formation and stabilization is achieved by coordination of the Lewis acid AlMe 3 , which also prevents formation of higher aggregated species. The feasibility of redox chemistry is shown with the plumbocene derivative Cp* 2 Pb, providing access to the corresponding monomeric Ln III half‐sandwich complexes [Cp*Ln(NR)(AlMe 3 )(thf) 2 ] (Ln=Sm, Yb).