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2522 J. Am. Chem. Soc. 1993, 115, 2522-2523 Importance of Electronic Geminal Interactions in
 

Summary: 2522 J. Am. Chem. Soc. 1993, 115, 2522-2523
Importance of Electronic Geminal Interactions in
Solvolysis Reactions. Application to the Determination
of the a-Silyl Effect on Carbenium Ion Stability
Yitzhak Apeloig,* Rivka Biton, and Awad Abu-Freih
Department of Chemistry, Technion-Israel
Institute of Technology,Haifn 32000, Israel
Received December 3, 1992
The relative stabilities of carbenium ions, e.g., RI+and R2+,
are often deduced from the solvolysis rates of the corresponding
R,X and R2X.' In doing so, it is often assumed that relative to
the energy difference between the carbenium ions the energy
difference between the reactants is insignificant.' While it is clear
that the presence of large steric or electronic interactions in the
precursors must be manifested in their solvolysisrate, this effect
has been demonstrated mostly for steric Despite
substantial recent evidence from experiment and from ab initio
calculations that electronic geminal interactions can be very large
even in neutral molecules (e.g., 17.4kcal/mol in CH2(0H)2,3their
significance to organic reactivity was discussed only in a few

  

Source: Apeloig, Yitzhak - Department of Chemistry, Technion, Israel Institute of Technology

 

Collections: Chemistry