Extended charge delocalization to 4-phenoxy substituent in benzhydryl solvolysis: possible contribution of non-canonical resonance structure in the cationic transition state
Journal
Journal of Physical Organic Chemistry
Journal Volume
15
Journal Issue
1
Pages
21--28
Date Issued
2001
Author(s)
Abstract
Abstract Solvolytic reactivities of 4‐nitrobenzhydryl bromides ( 2b – 5b ) and chlorides ( 2c – 5c ) were studied using single‐ and dual‐parameter Grunwald–Winstein‐type correlation analyses with Y BnX and Y x BnX scales, respectively. Extended charge delocalization over two aryl rings at cationic transition states were found for 3 and 5 , but not for 2 or 4 . Calculations of the charge distributions in 3c and in the corresponding cation 3a were performed using a Hartree–Fock approximation (RHF/6‐31G* basis set) and density functional models (pBP/DN** and other basis sets), respectively, on Mulliken population analysis and on electrostatic potential analysis. The possible contribution of non‐canonical resonance structure is discussed. Copyright © 2001 John Wiley & Sons, Ltd.
Type
journal article