Gas-phase association reactions of trimethylsilylium ((CH3)3Si+) with organic bases

Stone, John A.

doi:10.1002/(sici)1098-2787(1997)16:1<25::aid-mas2>3.0.co;2-c

Cited by 46 publications

(5 citation statements)

References 104 publications

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“…861 Å). As a matter of fact, the enthalpy of reaction (1) Si(CH 3 ) 3 + (g) + Si(CH 3 ) 4 (g) Si 2 (CH 3 ) 7 + (g) (1) measured experimentally using high-pressure mass spectrometry techniques by Stone and coworkers (-93.3 ± 1.7 kJ mol -1 ) [68,69], agrees very well with the calculated value (97.1 kJ mol -1 ) obtained at the QCISD/6-311+G(d,p) level [44] for the dissociation energy of the C-Si bond in complex Si 2 (CH 3 ) 7 + (the reverse of reaction 1). This initial impression was ratified by the fact that the corresponding molecular graph, obtained by means of the AIM theory (See Fig.…”

Section: Pentacovalent Carbon Atomssupporting

confidence: 84%

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Gámez¹,

Corral²,

Mó³

et al. 2010

COC

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An overview of recent studies, which show the important role played by computational chemistry in explaining and predicting the behavior of a great variety of systems is presented. The first example illustrates the useful interplay experiment-theory which allowed to unambiguously characterize the X2(CH3)7 + (X = Si, Ge, Sn, Pb) cations as paradigmatic examples of molecular systems involving pentacovalently bound carbon atoms. Also, the possibility of deeply analyzing the bonding in molecular systems, led to a rationalization of the quite different behavior of acetylene and iminoborane derivatives, in spite of being isoelectronic species. Similarly, the analysis of the bonding perturbations usually associated with ion-molecule interactions in the gas phase, or with protonation and deprotonation processes, has made possible the characterization of non-conventional complexes as the key structures in the interactions of unsaturated and aromatic Si and Ge containing compounds with transition metal ions or to explain the dramatic enhanced acidity of alkylboranes and ,unsaturated borane derivatives.

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Section: Pentacovalent Carbon Atomssupporting

confidence: 84%

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Gámez¹,

Corral²,

Mó³

et al. 2010

COC

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“…A review of the interactions of the TMS cation with organic bases, with emphasis on thermochemistry has been published by Stone (1997).…”

Section: Mass Spectrometry Of Tms Derivatives ▪mentioning

confidence: 99%

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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This review describes the mass spectral fragmentation of trimethylsilyl (TMS) and related alkylsilyl derivatives used for preparing samples for analysis, mainly by combined gas chromatography and mass spectrometry (GC/MS). The review is divided into three sections. The first section is concerned with the TMS derivatives themselves and describes fragmentation of derivatized alcohols, thiols, amines, ketones, carboxylic acids and bifunctional compounds such as hydroxy‐ and amino‐acids, halo acids and hydroxy ethers. More complex compounds such as glycerides, sphingolipids, carbohydrates, organic phosphates, phosphonates, steroids, vitamin D, cannabinoids, and prostaglandins are discussed next. The second section describes intermolecular reactions of siliconium ions such as the TMS cation and the third section discusses other alkylsilyl derivatives. Among these latter compounds are di‐ and trialkyl‐silyl derivatives, various substituted‐alkyldimethylsilyl derivatives such as the tert‐butyldimethylsilyl ethers, cyclic silyl derivatives, alkoxysilyl derivatives, and 3‐pyridylmethyldimethylsilyl esters used for double bond location in fatty acid spectra. © 2019 Wiley Periodicals, Inc. Mass Spec Rev 0000:1–107, 2019

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“…Once formed and accelerated, this ion can detach either tert-Butyl group to form the protonated radical ion m/z 299, or it can detach one of the two connected benzyl groups to form the product ion m/z 278, which presents a tri-coordinated silicon ion. Tri-coordinated silicon ions are very well known in gas phase mass spectrometric studies [29,30]. Moreover, another possible product ion can be formed as a result of the MS/MS fragmentation, when the indol moiety is released to form ion m/z 239.…”

Section: Characteristics Of the Obtained Organic Compounds Using Mass...mentioning

confidence: 99%

Advanced Mass Spectrometric Techniques for the Comprehensive Study of Synthesized Silicon-Based Silyl Organic Compounds: Identifying Fragmentation Pathways and Characterization

Rogowska,

Szultka-Młyńska,

Kanawati

et al. 2023

Materials

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The primary objective of this study was to synthesize and characterize novel silicon-based silyl organic compounds in order to gain a deeper understanding of their potential applications and interactions with other compounds. Four new artificial silyl organic compounds were successfully synthesized: 1-O-(Trimethylsilyl)-2,3,4,6-tetra-O-acetyl-β-d-glucopyranose (compound 1), 1-[(1,1-dimethylehtyl)diphenylsilyl]-1H-indole (compound 2), O-tert-butyldiphenylsilyl-(3-hydroxypropyl)oleate (compound 3), and 1-O-tert-Butyldiphenylsilyl-myo-inositol (compound 4). To thoroughly characterize these synthesized compounds, a combination of advanced mass spectrometric techniques was employed, including nanoparticle-assisted laser desorption/ionization mass spectrometry (NALDI-MS), Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and triple quadrupole electrospray tandem mass spectrometry (QqQ ESI-MS/MS). These analytical methods enabled the accurate identification and characterization of the synthesized silyl organic compounds, providing valuable insights into their properties and potential applications. Furthermore, the electrospray ionization–Fourier transform ion cyclotron resonance–tandem mass spectrometry (ESI-FT-ICR-MS/MS) technique facilitated the proposal of fragmentation pathways for the ionized silyl organic compounds, contributing to a more comprehensive understanding of their behavior during mass spectrometric analysis. These findings suggest that mass spectrometric techniques offer a highly effective means of investigating and characterizing naturally occurring silicon-based silyl organic compounds, with potential implications for advancing research in various fields and applications in different industries.

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Gas-phase association reactions of trimethylsilylium ((CH3)3Si+) with organic bases

Cited by 46 publications

References 104 publications

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Advanced Mass Spectrometric Techniques for the Comprehensive Study of Synthesized Silicon-Based Silyl Organic Compounds: Identifying Fragmentation Pathways and Characterization

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