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

Artículo

Autoría

DEFONSI LESTARD, MARIA ELIANA ; Tuttolomondo, María Eugenia ; Varetti, Eduardo Lelio ; Wann, Derek A. ; Robertson, Heather E. ; Rankin, David W. H. ; BEN ALTABEF, AIDA

Fecha

2010

Editorial y Lugar de Edición

ELSEVIER SCIENCE BV

Revista

JOURNAL OF MOLECULAR STRUCTURE, vol. 984 (pp. 376-382) - ISSN 0022-2860
ELSEVIER SCIENCE BV

ISSN

0022-2860

Resumen Información suministrada por el agente en SIGEVA

The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF3SO2OSi(CH3)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... The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF3SO2OSi(CH3)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 lpp[O bonded to Si)] ? r [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.

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Palabras Clave

Ab initio calculationsVibrational spectroscopyGas electron diffractionDFT calculations

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http://hdl.handle.net/11336/285270