Der Einfluss von Substituenten in Stellung 4 auf das n-Ionisationspotential des Chinuclidins

✍ Scribed by Gerhard Bieri; Edgar Heilbronner

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: German
• Weight: 356 KB
• Volume: 57
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19740570307

✦ Synopsis

Abstract

The vertical ‘lone‐pair’ ionization potentials I~v~(n) of fifteen 4‐substituted quinuclidines, of aza‐adamantane and of aza‐twistane have been determined by photoelectron spectroscopy. It is shown that the dependence of I~v~(n) on the nature of the substituent S can be rationalized in terms of the contribution to the local potential at the ionization site (i.e. the nitrogen centre) by the dipole of S. Both the solution p__K__'s and I~v~(n) correlate with classical substituent parameters (e. g. σ* or F) and with each other. However, no conclusions can be drawn from such regressions concerning a close relationship between the electronic mechanisms responsible for the observed changes in p__K__ or I~v~(n).