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Spectroscopic and Theoretical Investigations of Monocyclic Dioximes and Dimethoximes with Six‐, Eight‐, and Ten‐Membered Rings
Author(s) -
Strenge Andrea,
Rademacher Paul
Publication year - 1999
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199907)1999:7<1601::aid-ejoc1601>3.0.co;2-c
Subject(s) - chemistry , cyclooctane , ring (chemistry) , ab initio , computational chemistry , atomic orbital , molecule , molecular orbital , ab initio quantum chemistry methods , crystallography , stereochemistry , natural bond orbital , aromaticity , density functional theory , organic chemistry , quantum mechanics , physics , electron , catalysis
The dioximes 4–6 and the dimethoximes 7–9 , which contain the functional groups in opposite positions of a six‐, eight‐, or ten‐membered ring, were synthesized. Their conformational properties and transannular interactions were investigated by spectroscopic (PE, 13 C NMR) and theoretical (MMX, AM1, ab initio HF, and B3LYP) methods. While the cyclooctane derivatives 5 and 8 have conformations favourable for through‐space interactions of the π(CN) orbitals, in the other compounds no such interactions can be ascertained. Through‐space orbital interactions in the molecules with an eight‐membered ring lead to a splitting of the π(CN) MOs of 0.4 eV.