Investigation of the gas-phase structure and rotational barrier of trimethylsilyl trifluoromethanesulfonate and comparison with covalent sulfonates

M.E. Defonsi Lestard, M.E. Tuttolomondo, E.L. Varetti, D.A. Wann, H.E. Robertson, D.W.H. Rankin, A.B. Altabef

Research output: Contribution to journalArticlepeer-review

Abstract

The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF 3SO 2OSi(CH 3) 3, has been determined in the gas phase from electron-diffraction data supplemented by ab initio (MP2) and DFT calculations using 6-31G(d), 6-311++G(d,p) and 6-311G++(3df,3pd) basis sets. Both experimental and theoretical data indicate that only one gauche conformer is possible by rotating about the O-S bond. The anomeric effect is a fundamental stereoelectronic interaction and presents a profound influence on the electronic geometry. We have investigated the origin of the anomeric effect by means of NBO and AIM analysis. A natural bond orbital analysis showed that the lpπ[O bonded to Si)] → σ[C-S] hyperconjugative interaction favors the gauche conformation. In addition, comparison of the structural and stereoelectronic properties of the title molecule with those of silyl trifluoromethanesulfonate and methyl trifluoromethanesulfonate has been carried out. © 2010 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)376-382
JournalJOURNAL OF MOLECULAR STRUCTURE
Volume984
Issue number1-3
DOIs
Publication statusPublished - 15 Dec 2010

Bibliographical note

Export Date: 1 October 2013

Source: Scopus

CODEN: JMOSB

doi: 10.1016/j.molstruc.2010.10.009

Language of Original Document: English

Correspondence Address: Altabef, A. B.; INQUINOA - CONICET, Instituto de Química Física, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN S. M. de Tucumán, Argentina; email: altabef@fbqf.unt.edu.ar

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Keywords

  • ab initio calculations
  • DFT calculations
  • Fourier-type expansion
  • Gas electron diffraction
  • Internal barrier to rotation
  • Natural bond orbital analysis
  • Ab initio calculations
  • DFT calculation
  • Fourier
  • Calculations
  • Electron diffraction
  • Rapid thermal annealing
  • Rotation
  • Sulfur compounds

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