Steric isotope effects gauged by the bowl-inversion barrier in selectively deuterated pentaarylcorannulenes

Journal of the American Chemical Society
Tomoharu HayamaJay S Siegel

Abstract

Motivated by a greater bowl depth and barrier to bowl inversion in sym-1,3,5,7,9-pentamanisylcorannulene compared to corannulene, an experimental plan is developed to measure the effective hydrogen/deuterium steric kinetic isotope effect (KIE). Symmetry arguments are used to design orthogonal isotope labeling patterns so that the barrier for the CD3 compound can be measured in the presence of the CH3 compound. This scheme eliminates the differential uncertainty in the temperature measurement by allowing both barriers to be measure in the same sample, which in turn reduces the error in determining the differential barrier. Ab initio computations corroborate the structure and isotope effect found experimentally. The predicted and determined steric KIE at 250 K is 1.08 (modified QUIVER at M06-2X/cc-pVDZ) and 1.22 +/- 0.06 (VT-NMR), respectively. The results stem from differences in zero-point energy of the CH and CD motions; however, the phenomenology makes the CD3 group appear effectively "stickier" than CH3. The more the C-H...X interaction steepens the well, the "stickier" C-D should appear to be relative to C-H--an important consideration for molecular recognition and one supported by stronger binding constants for deuterated ...Continue Reading

References

Feb 28, 2003·Organic Letters·Gunther H GrubeJay S Siegel
Sep 16, 2004·Journal of the American Chemical Society·Michael SeitzOliver Reiser
Jul 2, 2005·The Journal of Organic Chemistry·Marina A PetrukhinaLawrence T Scott
Jan 28, 2006·The Journal of Chemical Physics·Stefan Grimme
Feb 24, 2006·Chemical Communications : Chem Comm·Zachary R LaughreyBruce C Gibb
Jul 28, 2007·Journal of the American Chemical Society·Martin SaundersOlga Kronja
Nov 1, 1947·The Journal of Physical and Colloid Chemistry·J BIGELEISEN

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Citations

Feb 23, 2013·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Aaron FongDaniel J O'Leary
Mar 26, 2016·Journal of the American Chemical Society·Yun LiuAmar H Flood
Aug 5, 2015·Inorganic Chemistry·Jackson K CherutoiAndrew W Maverick
Jul 30, 2010·Chemistry : a European Journal·Thomas Giagou, Matthew P Meyer
May 1, 2012·Chemical Communications : Chem Comm·Alla PogoreltsevEhud Keinan
Jul 22, 2019·Angewandte Chemie·Yu-Min LiuYuan-Zhi Tan
Apr 16, 2010·Angewandte Chemie·Jeffrey S MugridgeKenneth N Raymond
Mar 4, 2011·Angewandte Chemie·Daniel J O'LearyMatthew P Meyer
Aug 13, 2010·Journal of the American Chemical Society·Charles L Perrin, Phaneendrasai Karri
Jun 8, 2021·Chemical Science·Ephrath SolelEhud Keinan
Sep 6, 2012·Journal of the American Chemical Society·Maria N Eliseeva, Lawrence T Scott
Dec 8, 2011·Journal of the American Chemical Society·Jeffrey S MugridgeKenneth N Raymond
Dec 15, 2018·The Journal of Organic Chemistry·Wai-Shing WongHak-Fun Chow

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