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Molecular and Electronic Structure and Gas‐Phase Pyrolytic Generation of 7,7′‐Dioxasesquinorbornenes
Author(s) -
Antol Ivana,
EckertMaksić Mirjana,
Margetić Davor,
Maksić Zvonimir B.,
Kowski Klaus,
Rademacher Paul
Publication year - 1998
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(199807)1998:7<1403::aid-ejoc1403>3.0.co;2-g
Subject(s) - chemistry , pyrolytic carbon , molecule , decomposition , gas phase , neutron diffraction , crystallography , computational chemistry , stereochemistry , crystal structure , pyrolysis , organic chemistry
Structural and photoelectron spectroscopic (PES) features of 7,7′‐dioxa analogs of syn ‐ ( syn ‐ 2 ) and anti ‐sesquinor‐bornenes ( anti ‐ 2 ) are investigated. It is shown that the B3LYP‐6‐31G* and B3PW91/6‐31G* DFT methods are well‐suited for studying the geometrical properties of large organic molecules containing nonplanar double bonds, as is evident from comparisons with MP2/6‐31G* results and the available neutron diffraction and X‐ray data. It is also shown that the anti isomer is less stable than the syn isomer of 2 , in accordance with the stability ordering of syn ‐ 1 and anti ‐ 1 . Finally, PES evidence for the formation of anti ‐ 2 upon pyrolytic decomposition of the corresponding β‐lactone is given and discussed.