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Fourier Transform Ion Cyclotron Resonance Spectrometric Studies of Lewis Acid-Base Chemistry in Monochlorosilane

Murthy, Srihari and Beauchamp, J. L. (1995) Fourier Transform Ion Cyclotron Resonance Spectrometric Studies of Lewis Acid-Base Chemistry in Monochlorosilane. Journal of Physical Chemistry, 99 (22). pp. 9118-9121. ISSN 0022-3654. doi:10.1021/j100022a025. https://resolver.caltech.edu/CaltechAUTHORS:20180525-124927840

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Abstract

Fourier transform ion cyclotron resonance spectrometry is used to determine reaction pathways and rate constants for the reactions of the Lewis acids, SiH_nCl_(3-n)^+ (n = 1-3), with SiH_3Cl. SiH_2Cl^+ is observed to participate in both an H^- transfer reaction and a disproportionation reaction with SiH_3Cl. The ions SiH_3^+ and SiHCl_2^+ are observed to participate in only H^- transfer reactions with SiH_3Cl. The H^- affinity of SiH_2-Cl^+ is determined to be 1.4 ± 0.3 kcal mol^(-1) greater than that of SiHCl_2^+. Within experimental uncertainty, the values of the H^- affinities of the chlorosilyl ions lie within 1.7 kcal mol^(-1) of each other and decrease in the order SiH_2Cl^+ ≈ SiCl_3^+ > SiHCl_2^+. The disilylchloronium ion, (SiH_3)_2Cl^+, is proposed to be an intermediate complex in the reaction of SiH_3^+ with SiH_3Cl. Here, (SiH_3)_2Cl^- is formed through the reaction of protonated SiH_3Cl with SiH_3Cl. It is stable at room temperature at least on the order of tenths of seconds. By use of previously reported thermochemical data, the ionization potential of SiH_2Cl and the hydride affinity of SiH_2Cl^+ are derived to be 7.66 ± 0.23 eV and 251.2 ± 5.1 kcal mol^(-1), respectively.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/j100022a025DOIArticle
ORCID:
AuthorORCID
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 1995 American Chemical Society. Received: January 24, 1995; In Final Form: March 20, 1995. This work was supported by Grant CHE-91-08318 from the National Science Foundation. The assistance of Kathleen L. Walker in making available the SiH_3Cl sample used in these experiments is gratefully acknowledged.
Funders:
Funding AgencyGrant Number
NSFCHE-91-08318
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics8748
Issue or Number:22
DOI:10.1021/j100022a025
Record Number:CaltechAUTHORS:20180525-124927840
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180525-124927840
Official Citation:Fourier Transform Ion Cyclotron Resonance Spectrometric Studies of Lewis Acid-Base Chemistry in Monochlorosilane Srihari Murthy and J. L. Beauchamp The Journal of Physical Chemistry 1995 99 (22), 9118-9121 DOI: 10.1021/j100022a025
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86628
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2018 20:13
Last Modified:15 Nov 2021 20:40

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