The Design of "Neutral" Carbanions with Intramolecular Charge Compensation

The Journal of Organic Chemistry
Chaitanya S WannereHenry F Schaefer

Abstract

Strategies to construct zwitterionic anions from the parent anions are proposed. Two principles are employed; the cationic counterpart is (a) attached as a substituent or (b) inserted as an integral part at a remote location in the assembly. The optimized geometries reveal that a striking similarity exists between the zwitterions and the respective precursor parent anion. The computed vibrational frequencies emphasize that these novel entities are minima on their respective potential energy surfaces. A substantial HOMO-LUMO gap indicates that the proposed structures do not show instability in their respective electronic states and that the higher energy configuration states do not contribute to the ground state viability. The separation of charge between the monopoles in these zwitterions is demonstrated by moderately large nonzero dipole moments. Significant large energy barriers for rearrangement to the closely related positional isomers, demonstrated in a few cases, advocate the thermal stability (associated with spectroscopic viability) of the novel molecules. The donor capacity (basicity) of the anionic subunit in these zwitterions is comparable to that of the respective parent anions. Since the qualitative and quantitativ...Continue Reading

References

Jun 15, 1992·Physical Review. B, Condensed Matter·J P Perdew, Y Wang
Jun 14, 2000·Cancer Biotherapy & Radiopharmaceuticals·T R TheodoreR H Carpenter
Jul 12, 1996·The Journal of Organic Chemistry·Wei-Zhong Liu, Frederick G. Bordwell
Oct 24, 2001·Inorganic Chemistry·Roman G. KultyshevSheldon G. Shore
Nov 17, 2001·Chemical Reviews·R V Williams
Jul 18, 2002·Chemical Communications : Chem Comm·Olivier Siri, Pierre Braunstein
Sep 14, 2002·The Journal of Organic Chemistry·Frank StahlNorman L Allinger
Mar 12, 2005·The Journal of Organic Chemistry·Peter K Freeman
Oct 13, 2005·Chemical Reviews·Zhongfang ChenPaul von Ragué Schleyer
Feb 24, 2006·Organic Letters·Hossein Fallah-Bagher-ShaidaeiPaul v R Schleyer
May 26, 2006·Proceedings of the National Academy of Sciences of the United States of America·Bindu PillaiMichael N G James
Jul 21, 2006·The Journal of Physical Chemistry. B·Lionel SanguinetBenoît Champagne
Mar 8, 2007·Journal of Computational Chemistry·Veronika KasalováAttila G Császár
Aug 8, 2008·Angewandte Chemie·Roald HoffmannHenry F Schaefer

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Citations

Sep 26, 2017·Angewandte Chemie·Nema HafeziMark Mascal
Sep 12, 2018·Journal of the American Chemical Society·Priyakumari Chakkingal Parambil, Roald Hoffmann

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