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Activation of CS 2 and CO 2 by Silylium Cations
Author(s) -
Jenne Carsten,
Nierstenhöfer Marc C.,
Lessen Valentin
Publication year - 2021
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.202005003
Subject(s) - chemistry , silane , hydride , valence (chemistry) , ion , cascade , crystal structure , gas phase , molecule , methane , single crystal , crystallography , inorganic chemistry , hydrogen , organic chemistry , chromatography
The hydride‐bridged silylium cation [Et 3 Si−H−SiEt 3 ] + , stabilized by the weakly coordinating [Me 3 NB 12 Cl 11 ] − anion, undergoes, in the presence of excess silane, a series of unexpected consecutive reactions with the valence‐isoelectronic molecules CS 2 and CO 2 . The final products of the reaction with CS 2 are methane and the previously unknown [(Et 3 Si) 3 S] + cation. To gain insight into the entire reaction cascade, numerous experiments with varying conditions were performed, intermediate products were intercepted, and their structures were determined by X‐ray crystallography. Besides the [(Et 3 Si) 3 S] + cation as the final product, crystal structures of [(Et 3 Si) 2 SMe] + , [Et 3 SiS(H)Me] + , and [Et 3 SiOC(H)OSiEt 3 ] + were obtained. Experimental results combined with supporting quantum‐chemical calculations in the gas phase and solution allow a detailed understanding of the reaction cascade.