Ion-Molecule reactions in volatile silanes

Elucidating the structures of isomeric silylenium ions (SiC3H9+, SiC4H11+, SiC5H13+) by using specific ion/molecule reactions

“…SiHACH 3 ); _x+ C 3H 6 --->SiH x -1 (CH 3 )L x+ C 2H 4 (4) reflect the high proclivity of organosilicon ions to rearrange, consistent with their rich chemistry [1][2][3][4]. Except for a few notable examples [6,7), reaction mechanisms involving organosilicon ions are poorly understood, even though labeling experiments have been exploited in many cases.…”

“…oth cationic and anionic organosilicon species are highly reactive in the gas phase [1][2][3][4], with a number of interesting facile rearrangements occurring. For example, collision-activated dissociation (CAD) of Si(CH a); results in significant elimination of C 2H 4 , process 1 [5].…”

Chemistry and Thermochemistry of Silicon-Containing Anions in the Gas Phase

“…Computational studies suggested that the relative amount of [RlOH A recent study by Brauman and co-workers determined the relative amounts of proton abstraction versus siliconate formation in the reaction of HO" and (CH3)3SiCH2C(CH3)20H. 121 This reaction, which gives only the ionic product (CH3)3SiO-, could occur either (1) by proton abstraction at OH followed by 0" attack at silicon and subsequent /3-elimination of (CH3)2C=CH2 or (2) by direct siliconate formation and its subsequent decomposition to (CH3)3SiO" and (CH3)3COH. When HOenriched in 180 was used, it was determined that the rate of deprotonation was roughly 50% of the rate of direct siliconate formation.…”

“…Reviews of both gas-phase positive and negative ion silicon chemistry have been published. [1][2][3][4] In considering only negative ion silicon chemistry in the present review, one of our major goals is to emphasize the application of negative ion gas-phase chemistry as a tool that reveals otherwise difficult to obtain information about silicon-containing species. Since our reviews of gas-phase negative ion silicon work in 1987,1990, and 1993,3-5 additional silicon studies have been undertaken.…”

Potential Energy Surface of the Dimethylsilylium Cation and Mechanism of the Isomer Interconversion

“…Silylium (aka silylenium or silicenium) cations are well-known species of considerable stability in the gas phase. Many chemical reactions of these ions have been studied. − However, silylium ions have still eluded structural characterization by experimental methods, although numerous studies of their reactions, especially by collision-activated rearrangement and dissociation, allowed suggestion of the existence of different isomeric forms of these cations and their interconversion.…”