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Heterobimetallic Rare Earth–Lithium Complexes with Fewer Than Three Binaphtholates
Author(s) -
Sircoglou Marie,
Yang Jing,
Guillot Régis,
BezzenineLafollée Sophie,
Gandon Vincent
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300201
Subject(s) - chemistry , stoichiometry , alkali metal , adduct , lithium (medication) , rare earth , catalysis , crystallography , solid state , alkaline earth metal , ligand (biochemistry) , inorganic chemistry , medicinal chemistry , organic chemistry , mineralogy , medicine , biochemistry , receptor , endocrinology
Heterobimetallic rare earth–alkali metal binaphtholates (REMBs) are exquisite catalysts for asymmetric synthesis (Shibasaki catalysts). All solid‐state structures reported so far correspond to the general formula M 3 RE[( S )‐binolate] 3 (RE/M/B = 1:3:3 stoichiometry). We have synthesized and characterized crystallographically new complexes of this category, namely Li 3 RE[( S )‐binolate] 3 · x THF [RE = Sc ( 2 ), Sm ( 3 )] and Li 3 Nd[( S )‐binolate] 3 · 6THF · LiCl ( 4 ). The latter is the first reported adduct between a REMB and LiCl. We have also crystallized a rare type of REMB of 1:2:2.5 stoichiometry: Li 4 Sm 2 [( S )‐binolate] 5 · 6THF · 2H 2 O ( 5 ). Such a complex has only one precedent in the literature. The use of ( S )‐3,3′‐dimesityl‐1,1′‐binaphthyl‐2,2′‐diol ( 6 ) as ligand precursor allowed us to obtain the first X‐ray structures of unprecedented REMBs of 1:1:1 and 1:1:2 stoichiometries: {[( S )‐ 6 ]RECl 2 (THF) 2 }[Li(THF) 2 ] [RE = Y ( 7 ), Sm ( 8 )] and LiY[( S )‐ 6 ] 2 · 2THF ( 9 ).