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Construction of Inorganic Crown Ethers by s‐Block‐Metal‐Templated Si−O Bond Activation
Author(s) -
Dankert Fabian,
Richter RomanMalte,
Weigend Florian,
Xie Xiulan,
Balmer Markus,
Hänisch Carsten
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202014822
Subject(s) - chemistry , metal , nucleophile , crystallography , nuclear magnetic resonance spectroscopy , proton , crystal structure , stereochemistry , inorganic chemistry , catalysis , organic chemistry , physics , quantum mechanics
We herein report the synthesis, structures, coordination ability, and mechanism of formation of silicon analogs of crown ethers. An oligomerization of 2 D 2 ( I ) ( 2 D n ,=(Me 4 Si 2 O) n ) was achieved by the reaction with GaI 3 and MI x (M=Li, Na, Mg, Ca, Sr). In these reactions the metal cations serve as template and the anions (I − /[GaI 4 ] − ) are required as nucleophiles. In case of MI x =LiI, [Li( 2 D 3 )GaI 4 ] ( 1 ) is formed. In case of MI x =NaI, MgI 2 , CaI 2 , and SrI 2 the compounds [M( 2 D 4 )(GaI 4 ) x ] (M=Mg 2+ ( 3 ), Ca 2+ ( 4 ), Sr 2+ ( 5 ) are obtained. Furthermore the proton complex [H( 2 D 3 )][Ga 2 I 7 ] ( 6 ) was isolated and structurally characterized. All complexes were characterized by means of multinuclear NMR spectroscopy, DOSY experiments and, except for compound 3 , also by single crystal X‐ray diffraction. Quantum chemical calculations were carried out to compare the affinity of M + to 2 D n and other ligands and to shed light on the formation of larger rings from smaller ones.