High Resolution Infrared and Coherent Raman Studies of Propellane
EMSL Project ID
20907
Abstract
Propellane is one of the most exotic of all cyclic hydrocarbon, representing a case of extreme ring strain and the only known molecule with the bridgehead carbon atoms forming four bonds in the same hemisphere. Previous infrared work on propellane1 was limited to 0.06 cm-1 instrumental resolution, with a pressure broadened sample so that the effective overall resolution was less than 0.1 cm 1. This proposed work would study a great many more vibrational bands and would increase the precision of the one previously studied vibrational-rotational band by a factor of at least one hundred. We will be taking high-resolution (0.0015 cm-1) infrared spectra of propellane (C5H6) in order to obtain accurate band origins and rovibrational constants. Complementary high resolution Coherent Raman spectra will be obtained at Oregon State University as part of this collaboration. The resultant spectral parameters will yield greatly improved structural and potential parameters of this most unusual molecule. The analysis will result in at least two publications and will be the topic for a number of conference posters/presentations. The vibrational bands ranging from 400-3300 cm-1 will be studied. This work will utilize the IFS 120HR and 125HR infrared spectrometers and both the 20 cm short infrared sample cell and the variable pathlength White cell, all located at the EMSL facility. Far infrared spectra (below 600 cm-1) will require a liquid helium cooled bolometer. The fundamental vibrations we wish to investigate are located in four different spectral regions. Because of this, the spectrometer usage required for this project should be relatively minimal.
The propellane sample will be synthesized with the assistance of Dr. Tim Hubler at PNNL. The procedure for synthesizing propellane2 (solvent free) is found in the literature and can be accomplished in a few steps now that the main precursor in the synthesis is commercially available.
1. Wiberg, K. B.; Walker, F. H. Journal of the American Chemical Society 1982, 104, 5239.
2. Belzner, J.; Bunz, U.; Semmler, K.; Szeimies, G.; Opitz, K.; Schluter, A. D. Chemische Berichte 1989, 122, 397.
Project Details
Project type
Exploratory Research
Start Date
2006-07-17
End Date
2007-07-19
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Kirkpatrick RW, T Masiello, N Jariyasopit, A Weber, JW Nibler, A Maki, TA Blake, and TL Hubler. 2008. "High Resolution Infrared Spectroscopy of [1.1.1] Propellane." Journal of Molecular Spectroscopy 248(2):153-160.
Kirkpatrick RW, T Masiello, N Jariyasopit, JW Nibler, AG Maki, TA Blake, and A Weber. 2009. "High-resolution rovibrational study of the Coriolis-coupled nu(12) and nu(15) modes of [1.1.1]propellane." Journal of Molecular Spectroscopy 253(1):41-50.
Maki A, A Weber, JW Nibler, T Masiello, TA Blake, and RW Kirkpatrick. 2010. "High resolution infrared spectroscopy of [1.1.1]propellane: the region of the v9 band." Journal of Molecular Spectroscopy 264(1):26-36. doi:10.1016/j.jms.2010.08.008