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Title:Structural Isomerization Of The Gas Phase 2-norbornyl Cation Revealed With Infrared Spectroscopy And Computational Chemistry
Author(s):Mauney, Daniel
Contributor(s):Duncan, Michael A; Mosley, Jonathan
Subject(s):Mini-symposium: Beyond the Mass-to-Charge Ratio: Spectroscopic Probes of the Structures of Ions
Abstract:\begin{wrapfigure}{l}{0pt} \includegraphics[scale=0.3]{TOC_Graphic.eps} \end{wrapfigure} The non-classical structure of the 2-norborny cation (\chem{C_7H_{11}}$^{+}$) which was at the center of "the most heated chemical controversy of our time"\footnote{Schleyer,P.v.R. et. al.; Stable Carbocation Chemistry, John Wiley \& Sons,Inc.; New York, 1997, Cahpter 2} has been observed in the condensed phase and recently using X-ray crystallography. However, no gas phase vibrational spectrum has been collected. The \chem{C_7H_{11}}$^{+}$ cation is produced via \chem{H_3}$^{+}$ protonation of norbornene by pulsed discharge in a supersonic expansion of \chem{H_2}/Ar. Ions are mass-selected and probed using infrared photodissociation spectroscopy. Due to high exothermicity, protonation via \chem{H_3}$^{+}$ leads to a structural isomerization to the global minimum structure 1,3-dimethylcyclopentenyl (DMCP$^{+}$). Experiments are currently being conducted to find softer protonation techniques that could lead to the authentic 2-norbornyl cation.
Issue Date:2014-06-17
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:Mauney, D.; Duncan, M.A.; Mosley, J. STRUCTURAL ISOMERIZATION OF THE GAS PHASE 2-NORBORNYL CATION REVEALED WITH INFRARED SPECTROSCOPY AND COMPUTATIONAL CHEMISTRY. Proceedings of the International Symposium on Molecular Spectroscopy, Urbana, IL, June 16-21, 2014. DOI: 10.15278/isms.2014.TG10
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/50854
DOI:10.15278/isms.2014.TG10
Rights Information:Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/
Date Available in IDEALS:2014-09-17
2015-04-14


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