ISSN:
1434-193X
Keywords:
Azaallenium ions
;
Azaallylium ions
;
Iminium ion
;
Kinetics
;
Linear Free Energy Relationships
;
Ab initio calculations
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
---The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≍ -16 and E(3+) = -10.43 were obtained. They show that the relative reactivities of these ions are approximately 1012:1:106. Quantum chemical calculations (ab initio, DFT) of the methyl anion affinities for the ions 1b+,2a+ and3+ are in agreement with the experimental E values. The X-ray structure of 3+·CF3SO3- is reported for the first time; it shows no strong interaction between the cation and the anion.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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