Home > Publications database > A Novel Approach in Analyzing Aromaticity by Homo- and Isostructural Reactions: An ab Initio Study of Fluorobenzenes > print

001     51224
005     20260213161809.0
024 7 _ |2 pmid
|a pmid:16834316
024 7 _ |2 DOI
|a 10.1021/jp0532871
024 7 _ |2 WOS
|a WOS:000233436900016
024 7 _ |2 Handle
|a 2128/2234
037 _ _ |a PreJuSER-51224
041 _ _ |a eng
082 _ _ |a 530
084 _ _ |2 WoS
|a Chemistry, Physical
084 _ _ |2 WoS
|a Physics, Atomic, Molecular & Chemical
100 1 _ |0 P:(DE-HGF)0
|a Baric, D.
|b 0
245 _ _ |a A Novel Approach in Analyzing Aromaticity by Homo- and Isostructural Reactions: An ab Initio Study of Fluorobenzenes
260 _ _ |a Washington, DC
|b Soc.
|c 2005
300 _ _ |a 10594
336 7 _ |0 PUB:(DE-HGF)16
|2 PUB:(DE-HGF)
|a Journal Article
336 7 _ |2 DataCite
|a Output Types/Journal article
336 7 _ |0 0
|2 EndNote
|a Journal Article
336 7 _ |2 BibTeX
|a ARTICLE
336 7 _ |2 ORCID
|a JOURNAL_ARTICLE
336 7 _ |2 DRIVER
|a article
440 _ 0 |0 3693
|a Journal of Physical Chemistry A
|v 109
|x 1089-5639
500 _ _ |a Record converted from VDB: 12.11.2012
520 _ _ |a The influence of fluorine substitutions on the stability of benzene is examined by using the Hartree-Fock (HF) and MP2 models. It is conclusively demonstrated that homodesmotic reactions based on the open-chain zigzag polyenes are unsatisfactory. A comparison of the intramolecular interactions of educts and products shows that they are not well balanced. Hence, these reactions should be abandoned in discussing aromaticity. A much better vehicle for exploring aromaticity is provided by homostructural reactions, which employ cyclic monoene and diene as reference model compounds. Their heavy atoms are enforced to assume planar geometries to enable sigma/pi separation. The HF/cc-pVTZ calculations show that extrinsic aromaticity of benzene B DeltaE(ease)(B)() arises both from the sigma- and pi-contributions. They are -14.8 and -23.1 in kcal/mol, respectively, if the stockholder energy partitioning scheme is employed. This result implies that both the sigma- and pi-frameworks contribute to the aromatic stabilization of B, the latter being more important. The total aromatic stabilization DeltaE(ease)(B)() is -37.9 kcal/mol. Schleyer's indene-isoindene isomerization approach also strongly indicates that the decisive factor in determining the aromatic stability of the benzene moiety is the pi-electron framework. The origin of extrinsic aromaticity is identified as the increased nuclear-electron attraction of both sigma- and pi-electrons, if 1,3-cyclohexadiene is used as a gauge compound. Further, by using a system of isostructural reactions, it is conclusively demonstrated that fluorobenzenes exhibit a remarkable additivity of the substituent effects, as far as the stability of multiply substituted benzenes is concerned. This additivity rule is so accurate that it enables delineation of the fluorine repulsions and the aromaticity defect DeltaE(AD). It appears that the DeltaE(AD) values increase upon sequential fluorine substitution at the next nearest (vicinal) position thus making multiply fluorinated benzenes less stable.
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|a Betrieb und Weiterentwicklung des Höchstleistungsrechners
|c I03
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|a Simulation and Data Laboratory Complex Particle Systems
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588 _ _ |a Dataset connected to Web of Science, Pubmed
650 _ 2 |2 MeSH
|a Butadienes: chemistry
650 _ 2 |2 MeSH
|a Chemistry, Physical
650 _ 2 |2 MeSH
|a Ethylenes: chemistry
650 _ 2 |2 MeSH
|a Fluorobenzenes: chemistry
650 _ 2 |2 MeSH
|a Hydrocarbons, Aromatic: chemistry
650 _ 2 |2 MeSH
|a Hydrocarbons, Cyclic: chemistry
650 _ 2 |2 MeSH
|a Hydrocarbons, Fluorinated: chemistry
650 _ 2 |2 MeSH
|a Models, Chemical
650 _ 2 |2 MeSH
|a Molecular Structure
650 _ 2 |2 MeSH
|a Physicochemical Phenomena
650 _ 7 |0 0
|2 NLM Chemicals
|a Butadienes
650 _ 7 |0 0
|2 NLM Chemicals
|a Ethylenes
650 _ 7 |0 0
|2 NLM Chemicals
|a Fluorobenzenes
650 _ 7 |0 0
|2 NLM Chemicals
|a Hydrocarbons, Aromatic
650 _ 7 |0 0
|2 NLM Chemicals
|a Hydrocarbons, Cyclic
650 _ 7 |0 0
|2 NLM Chemicals
|a Hydrocarbons, Fluorinated
650 _ 7 |0 106-99-0
|2 NLM Chemicals
|a 1,3-butadiene
650 _ 7 |0 74-85-1
|2 NLM Chemicals
|a ethylene
650 _ 7 |2 WoSType
|a J
700 1 _ |0 P:(DE-HGF)0
|a Kovacevic, B.
|b 1
700 1 _ |0 P:(DE-HGF)0
|a Maksic, Z. B.
|b 2
700 1 _ |0 P:(DE-Juel1)132204
|a Müller, T.
|b 3
|u FZJ
773 _ _ |0 PERI:(DE-600)2006031-2
|a 10.1021/jp0532871
|g Vol. 109, p. 10594
|p 10594
|q 109<10594
|t The @journal of physical chemistry / A
|v 109
|x 1089-5639
|y 2005
856 7 _ |u http://dx.doi.org/10.1021/jp0532871
|u http://hdl.handle.net/2128/2234
856 4 _ |u https://juser.fz-juelich.de/record/51224/files/80351.pdf
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|d 31.12.2007
|g ZAM
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|l Zentralinstitut für Angewandte Mathematik
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