Extended charge delocalization to 4‐phenoxy substituent in benzhydryl solvolysis: possible contribution of non‐canonical resonance structure in the cationic transition state | Zendy

Liu KwangTing | Zendy; Chuang ChihShiow | Zendy; Jin Bihyaw | Zendy

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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.

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