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The Role of Ion–Neutral Reorientation in the Unimolecular Reactivity of Metastable Electron-ionized Amines. Competing Influences of the Size of the Fragments and the Polarity of the Neutral

✍ Scribed by Pierre Longevialle; Odile Lefèvre

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 531 KB
Volume: 10
Category: Article
ISSN: 0951-4198
DOI: 10.1002/(sici)1097-0231(199604)10:6<621::aid-rcm513>3.0.co;2-y

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✦ Synopsis

New examples confirm that the competition between acleavages of ionized metastable amines is governed by the corresponding ion-neutral (I-N) reorientPton -rather than decompositioncritical energies. I-N reorientation critical energies essentially depend on two important factors: the size of the fragments ('size effect') and the polarity of the neutral ('polarity effect'). Examples are described showing the predominance of the size effect when the neutral has no permanent dipole and how the polarity effect takes over when more and more polar groups are introduced into the neutral. The reactivity of metastable amine radical cations is the result of the interplay of both effects.

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