Continued search for elusive persistent trivalent organosilyl cations: the claimed trimethylsilyl cation revisited. Attempted preparation of cyclic and halogen-bridged organosilicenium ions

1992 ◽  
Vol 114 (20) ◽  
pp. 7737-7742 ◽  
Author(s):  
George A. Olah ◽  
Golam Rasul ◽  
Ludger Heiliger ◽  
Joseph Bausch ◽  
G. K. Surya Prakash
Keyword(s):  
Trimethylsilyl Cation

Gas Phase Basicities of Styrenes toward Trimethylsilyl Cation. Structure and Stability of Me3Si-Styrene+Complexes

1992 ◽  
Vol 21 (12) ◽  
pp. 2439-2442 ◽  
Author(s):  
Masaaki Mishima ◽  
Chul Hyun Kang ◽  
Mizue Fujio ◽  
Yuho Tsuno
Keyword(s):  
Gas Phase ◽  
Structure And Stability ◽  
Trimethylsilyl Cation ◽  
Gas Phase Basicities

Ion Cyclotron Resonance Studies of Alkylsilyl Ions. II. The Reactions of Ketones, Carboxylic Acids and Esters with the Trimethylsilyl Cation

1979 ◽  
Vol 32 (6) ◽  
pp. 1389 ◽  
Author(s):  
IA Blair ◽  
JH Bowie
Keyword(s):  
Carboxylic Acid ◽  
Transition State ◽  
Lewis Acid ◽  
Cyclotron Resonance ◽  
Nucleophilic Attack ◽  
Ion Cyclotron Resonance ◽  
Deuterium Isotope Effect ◽  
Trimethylsilyl Cation ◽  
A Minor ◽  
Membered Transition State

Nucleophilic attack of a ketone, carboxylic acid or ester at the electrophilic centre of the trimethylsilyl cation (Me,Si+) produces a 1:1 adduct. This adduct does not decompose in the case of ketones. Acid adducts decompose primarily by loss of methane, but a minor pathway exists which involves elimination of a ketene. Ester adducts fragment primarily by this latter process through a four-membered transition state. The transfer of hydrogen was shown to arise solely from the acyl group and was shown to proceed with a small deuterium isotope effect. Further decomposition of the resulting ion by loss of methane provides unequivocal proof that esters react predominantly through the alkyl oxygen with the Lewis acid Me3Si+.

Free and associated trimethylsilyl cation in solution

1988 ◽  
pp. 455 ◽  
Author(s):  
Joseph B. Lambert ◽  
JoAnn A. McConnell ◽  
Wojciech Schilf ◽  
William J. Schulz
Keyword(s):  
Trimethylsilyl Cation

Smooth photogeneration of α,n-didehydrotoluenes (DHTs)

2013 ◽  
Vol 85 (7) ◽  
pp. 1479-1486 ◽  
Author(s):  
Stefano Protti ◽  
Davide Ravelli ◽  
Maurizio Fagnoni ◽  
Angelo Albini
Keyword(s):  
Chloride Ion ◽  
Biological Action ◽  
Trimethylsilyl Cation ◽  
Phenyl Cation

Irradiation of the three isomeric (chlorobenzyl)trimethylsilanes in methanol–water generates the corresponding didehydrotoluenes (DHTs). The process involves expulsion of a chloride ion to give the triplet phenyl cation and ensuing elimination of the trimethylsilyl cation. This straightforward generation of DHT intermediates overcomes a shortcoming of previous methodology (cycloaromatization of enyne-allenes), which is limited to the meta-isomer, and opens the path for understanding the chemistry (and possibly the biological action) of these unusual intermediates.

Sign in / Sign up

Export Citation Format

Share Document