Die π‐Donorfähigkeit schwerer Elemente ist nicht geringer
- 7 October 1996
- journal article
- zuschrift
- Published by Wiley in Angewandte Chemie
- Vol. 108 (19) , 2373-2376
- https://doi.org/10.1002/ange.19961081918
Abstract
In erster Linie von der Gruppe und weniger von der Periode hängt der stabilisierende Einfluß von Elektronenpaardonor‐Substituenten der ersten fünf Reihen des Periodensystems auf Carbokationen ab. Dies zeigen ab‐initio‐Rechnungen auf hohem Niveau (QCISD(T)/DZ+ +PP//MP2(fc)/DZ + P). Wird die EH2‐Planarisierung (E = Element der Gruppe 15) berücksichtigt, sind die Stabilisierungsenergien durch Substituenten der Gruppe 15 nahezu konstant (ca. 95 kcal mol−1 von N bis Sb relativ zu CH+3); sie übertreffen die Methylstabilisierungsenergien der Chalkogene (60–66 kcal mol−1, O < S ≈ Se < Te) und der Halogene (18–38 kcal mol−1, F < Cl ≈ Br < I).Keywords
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