Ground statevs.transition state substituent effects on reactions of aziridinium salts

Autor:	DeLanson R. Crist, Saleh A. Turujman, Joseph A. Hashmall
Rok vydání:	1991
Předmět:	Stereochemistry Organic Chemistry Binding energy Substituent chemistry.chemical_element Carbocation Ring (chemistry) Nitrogen Ion Bond length chemistry.chemical_compound chemistry Physical chemistry Ground state
Zdroj:	Journal of Heterocyclic Chemistry. 28:1993-1995
ISSN:	1943-5193 0022-152X
DOI:	10.1002/jhet.5570280834
Popis:	The possibility that the similarity of Hammett ρ values for several very different reactions of 2-arylaziridinium salts is due to ground state effects was investigated by MO methods and ESCA. Minimum energy structures of p-nitrophenyl-, phenyl-, and p-methoxyphenyl-substituted ions, however, have the same C2N bond lengths. This result shows that substituent effects are primarily a transition state phenomenon, even in the three-membered ring heterocycles. In agreement, the ground state does not have significant amino carbocation character based on similar charge distributions of 2-phenyl-N,N-dimethylaziridinium ion and N,N,N-trimethylbenzylammonium ion as well as the same nitrogen ls binding energies by ESCA studies on corresponding salts.
Databáze:	OpenAIRE
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