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
Full text is not posted in this repository. Consult Related URLs below.
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180525-124927840
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: |
| ||||||
ORCID: |
| ||||||
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: |
| ||||||
Other Numbering System: |
| ||||||
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 |
Repository Staff Only: item control page