ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The HE(Iα) photoelectron (PE) spectra of 2,3,5,6-tetramethylidene-2-bicyclo[2.2.1]heptanone (12), 5,6-dimethylidene-2-bicyclo[2.2.1]heptanone (14), 5,6-dimethylidene-2-bicyclo[2.2.2]octanone (16), and 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octanone (17) have been recorded, Comparison with the PE data of other β,γ-unsaturated ketones and parent alkenes, and with the result of ab initio STO-3G calculations, confirm the existence of significant interactions between the oxygen lone-pair orbital no and the double-bond π orbital(s). It is argued that the major contributions to the basis energy shifts and to the cross term between the no and π orbitals are due to a ‘through-bond’ mechanism.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19870700612