Activation of CS2 and CO2 by Silylium Cations.
Chemistry
; 27(10): 3288-3291, 2021 Feb 15.
Article
in En
| MEDLINE
| ID: mdl-33215771
ABSTRACT
The hydride-bridged silylium cation [Et3 Si-H-SiEt3 ]+ , stabilized by the weakly coordinating [Me3 NB12 Cl11 ]- anion, undergoes, in the presence of excess silane, a series of unexpected consecutive reactions with the valence-isoelectronic molecules CS2 and CO2 . The final products of the reaction with CS2 are methane and the previously unknown [(Et3 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 [(Et3 Si)3 S]+ cation as the final product, crystal structures of [(Et3 Si)2 SMe]+ , [Et3 SiS(H)Me]+ , and [Et3 SiOC(H)OSiEt3 ]+ were obtained. Experimental results combined with supporting quantum-chemical calculations in the gas phase and solution allow a detailed understanding of the reaction cascade.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2021
Document type:
Article
Affiliation country: