Measurements of the structure of methyltrioxorhenium using microwave spectroscopy

P. Wikrent, B. J. Drouin, Stephen G Kukolich, J. C. Lilly, M. T. Ashby, W. A. Herrmann, W. Scherer

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The rotational spectra for six isotopomers of methyltrioxorhenium (MTO) were measured in the 6-14 GHz range using a Flygare-Balle-type pulsed-beam microwave spectrometer. The measured transition frequencies were analyzed to obtain rotational constants and quadrupole coupling strengths. Rotational constants from the new measurements were used, along with previous results for the normal and 13C isotopomers, to determine the complete, three-dimensional structure for MTO. The bond lengths obtained are r(Re-C)=2.074(4) Å, r(Re-O)=1.703(2) Å, and r(C-H)=1.088(7) Å. The interbond angles are 〈Re-C-H=108.9(2)° and 〈C-Re-O =106.4(4)°. This complex appears to have C3v symmetry in the gas phase, unlike the solid-state structure. Structural parameters are compared with neutron-diffraction, electron-diffraction, and density functional theory results. Spectra for the asymmetric-top isotopomers were much more difficult to analyze due to effects of off-diagonal quadrupole coupling terms and possible internal rotation. The Re quadrupole coupling strength is increased by 1.4% for CD3ReO3 compared with CH3ReO3, illustrating a secondary isotope effect.

Original languageEnglish (US)
Pages (from-to)2187-2192
Number of pages6
JournalThe Journal of Chemical Physics
Volume107
Issue number7
StatePublished - Aug 15 1997

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Microwave spectroscopy
Microwave spectrometers
quadrupoles
microwaves
Bond length
Neutron diffraction
Electron diffraction
Isotopes
spectroscopy
Density functional theory
Carrier concentration
microwave spectrometers
Gases
rotational spectra
isotope effect
neutron diffraction
electron diffraction
vapor phases
density functional theory
solid state

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Wikrent, P., Drouin, B. J., Kukolich, S. G., Lilly, J. C., Ashby, M. T., Herrmann, W. A., & Scherer, W. (1997). Measurements of the structure of methyltrioxorhenium using microwave spectroscopy. The Journal of Chemical Physics, 107(7), 2187-2192.

Measurements of the structure of methyltrioxorhenium using microwave spectroscopy. / Wikrent, P.; Drouin, B. J.; Kukolich, Stephen G; Lilly, J. C.; Ashby, M. T.; Herrmann, W. A.; Scherer, W.

In: The Journal of Chemical Physics, Vol. 107, No. 7, 15.08.1997, p. 2187-2192.

Research output: Contribution to journalArticle

Wikrent, P, Drouin, BJ, Kukolich, SG, Lilly, JC, Ashby, MT, Herrmann, WA & Scherer, W 1997, 'Measurements of the structure of methyltrioxorhenium using microwave spectroscopy', The Journal of Chemical Physics, vol. 107, no. 7, pp. 2187-2192.
Wikrent P, Drouin BJ, Kukolich SG, Lilly JC, Ashby MT, Herrmann WA et al. Measurements of the structure of methyltrioxorhenium using microwave spectroscopy. The Journal of Chemical Physics. 1997 Aug 15;107(7):2187-2192.
Wikrent, P. ; Drouin, B. J. ; Kukolich, Stephen G ; Lilly, J. C. ; Ashby, M. T. ; Herrmann, W. A. ; Scherer, W. / Measurements of the structure of methyltrioxorhenium using microwave spectroscopy. In: The Journal of Chemical Physics. 1997 ; Vol. 107, No. 7. pp. 2187-2192.
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