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Extended charge delocalization to 4‐phenoxy substituent in benzhydryl solvolysis: possible contribution of non‐canonical resonance structure in the cationic transition state
Author(s) -
Liu KwangTing,
Chuang ChihShiow,
Jin Bihyaw
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.439
Subject(s) - chemistry , delocalized electron , mulliken population analysis , cationic polymerization , substituent , computational chemistry , basis set , charge density , charge (physics) , resonance (particle physics) , solvolysis , density functional theory , stereochemistry , atomic physics , organic chemistry , quantum mechanics , physics , hydrolysis
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.