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

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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
Publication statusPublished - Aug 15 1997

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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.