Construction of Inorganic Crown Ethers by s-Block-Metal-Templated Si-O Bond Activation.
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ABSTRACT: We herein report the synthesis, structures, coordination ability, and mechanism of formation of silicon analogs of crown ethers. An oligomerization of 2 D2 (I) (2 Dn ,=(Me4 Si2 O)n ) was achieved by the reaction with GaI3 and MIx (M=Li, Na, Mg, Ca, Sr). In these reactions the metal cations serve as template and the anions (I- /[GaI4 ]- ) are required as nucleophiles. In case of MIx =LiI, [Li(2 D3 )GaI4 ] (1) is formed. In case of MIx =NaI, MgI2 , CaI2 , and SrI2 the compounds [M(2 D4 )(GaI4 )x ] (M=Mg2+ (3), Ca2+ (4), Sr2+ (5) are obtained. Furthermore the proton complex [H(2 D3 )][Ga2 I7 ] (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 Dn and other ligands and to shed light on the formation of larger rings from smaller ones.
SUBMITTER: Dankert F
PROVIDER: S-EPMC8252370 | biostudies-literature |
REPOSITORIES: biostudies-literature
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