Ab Initio/GIAO-CCSD(T) Study of the Trimethyl- and Dimethylsilicenium Ions: Structures, 29Si, 13C, and 1H NMR Chemical Shifts, and IR Spectra

Golam Rasul; Jonathan L. Chen; G. K. Surya PrakashGeorge A. Olah

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Ab Initio/GIAO-CCSD(T) Study of the Trimethyl- and Dimethylsilicenium Ions: Structures, 29Si, 13C, and 1H NMR Chemical Shifts, and IR Spectra

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The C3h conformation of the trimethylsilicenium ion 1 was established to be the preferred global energy minimum structure based on energy calculations. Because C-H hyperconjugation occurs least favorably in this conformation of the analogous tert-butyl cation, it may not contribute in large part to the stabilization of this cation, especially given the ineffectiveness of the 3p-2sp3 overlap that would need to be involved. This is in contrast with the preferred Cs global energy conformers of the tert-butyl cation. The C2V structure 4 and C2 enantiomers 6 and 7 are the preferred conformations of the dimethylsilicenium ion based on energy comparison. None of these structures have C-H bonds ideally oriented for hyperconjugation with the empty p orbital of the cationic silicon, indicating that it does not likely stabilize the ion to any significant extent. The computed IR spectra and 29Si, 13C, and 1H NMR chemical shifts of the isomers were also discussed. Whereas the studied alkylsilicenium ions are thermodynamically stable, their observation as persistent ions in solution is much more difficult because of their kinetic instability toward varied electron-donating solvents.

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2010年第12期|4394-4399|共6页
作者
Golam Rasul; Jonathan L. Chen; G. K. Surya PrakashGeorge A. Olah;
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作者单位

Loker Hydrocarbon Research Institute and Department of Chemistry, UniVersity of Southern California, UniVersity Park, Los Angeles, California 90089-1661;

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正文语种英语
中图分类物理化学（理论化学）、化学物理学;
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Trimethyl; Structures; Chemical Shifts;

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Ab Initio/GIAO-CCSD(T) Study of the Trimethyl- and Dimethylsilicenium Ions: Structures, 29Si, 13C, and 1H NMR Chemical Shifts, and IR Spectra

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