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000051224 084__ $$2WoS$$aChemistry, Physical
000051224 084__ $$2WoS$$aPhysics, Atomic, Molecular & Chemical
000051224 1001_ $$0P:(DE-HGF)0$$aBaric, D.$$b0
000051224 245__ $$aA Novel Approach in Analyzing Aromaticity by Homo- and Isostructural Reactions: An ab Initio Study of Fluorobenzenes
000051224 260__ $$aWashington, DC$$bSoc.$$c2005
000051224 300__ $$a10594
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000051224 440_0 $$03693$$aJournal of Physical Chemistry A$$v109$$x1089-5639
000051224 500__ $$aRecord converted from VDB: 12.11.2012
000051224 520__ $$aThe 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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000051224 650_2 $$2MeSH$$aButadienes: chemistry
000051224 650_2 $$2MeSH$$aChemistry, Physical
000051224 650_2 $$2MeSH$$aEthylenes: chemistry
000051224 650_2 $$2MeSH$$aFluorobenzenes: chemistry
000051224 650_2 $$2MeSH$$aHydrocarbons, Aromatic: chemistry
000051224 650_2 $$2MeSH$$aHydrocarbons, Cyclic: chemistry
000051224 650_2 $$2MeSH$$aHydrocarbons, Fluorinated: chemistry
000051224 650_2 $$2MeSH$$aModels, Chemical
000051224 650_2 $$2MeSH$$aMolecular Structure
000051224 650_2 $$2MeSH$$aPhysicochemical Phenomena
000051224 650_7 $$00$$2NLM Chemicals$$aButadienes
000051224 650_7 $$00$$2NLM Chemicals$$aEthylenes
000051224 650_7 $$00$$2NLM Chemicals$$aFluorobenzenes
000051224 650_7 $$00$$2NLM Chemicals$$aHydrocarbons, Aromatic
000051224 650_7 $$00$$2NLM Chemicals$$aHydrocarbons, Cyclic
000051224 650_7 $$00$$2NLM Chemicals$$aHydrocarbons, Fluorinated
000051224 650_7 $$0106-99-0$$2NLM Chemicals$$a1,3-butadiene
000051224 650_7 $$074-85-1$$2NLM Chemicals$$aethylene
000051224 650_7 $$2WoSType$$aJ
000051224 7001_ $$0P:(DE-HGF)0$$aKovacevic, B.$$b1
000051224 7001_ $$0P:(DE-HGF)0$$aMaksic, Z. B.$$b2
000051224 7001_ $$0P:(DE-Juel1)132204$$aMüller, T.$$b3$$uFZJ
000051224 773__ $$0PERI:(DE-600)2006031-2$$a10.1021/jp0532871$$gVol. 109, p. 10594$$p10594$$q109<10594$$tThe @journal of physical chemistry <Washington, DC> / A$$v109$$x1089-5639$$y2005
000051224 8567_ $$uhttp://hdl.handle.net/2128/2234$$uhttp://dx.doi.org/10.1021/jp0532871
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