TY - JOUR
T1 - Consistent aromaticity evaluations of methylenecyclopropene analogues
AU - Wang, Yan
AU - Fernández, Israel
AU - Duvall, Matthew
AU - Wu, Judy I.Chia
AU - Li, Qianshu
AU - Frenking, Gernot
AU - Schleyer, Paul Von Ragué
PY - 2010/12/3
Y1 - 2010/12/3
N2 - Quantitative evaluations of the aromaticity (antiaromaticity) of neutral exocyclic substituted cyclopropenes (HC)2C=X (X = BH to InH (group 13), CH2 to SnH2 (group 14), NH to SbH (group 15), O to Te (group 16)) by their computed extra cyclic resonance energies (ECRE, via the block-localized wave function method) and by their aromatic stabilization energies (ASEs, via energy decomposition analyses) correlate satisfactorily (R2 = 0.974). Electronegative X-based substituents increase the aromaticity of the cyclopropene rings, whereas electropositive substituents have the opposite effect. For example, (HC)2C=O is the most aromatic (ECRE = 10.3 kcal/mol), and (HC)2C=InH is the most antiaromatic (ECRE = -15.0 kcal/mol). The most refined dissected nucleus-independent chemical shift magnetic aromaticity index, NICS(0)πzz, also agrees with both energetic indexes (R2 = 0.968, for ECRE; R2 = 0.974, for ASE), as do anisotropy of the induced current density plots.
AB - Quantitative evaluations of the aromaticity (antiaromaticity) of neutral exocyclic substituted cyclopropenes (HC)2C=X (X = BH to InH (group 13), CH2 to SnH2 (group 14), NH to SbH (group 15), O to Te (group 16)) by their computed extra cyclic resonance energies (ECRE, via the block-localized wave function method) and by their aromatic stabilization energies (ASEs, via energy decomposition analyses) correlate satisfactorily (R2 = 0.974). Electronegative X-based substituents increase the aromaticity of the cyclopropene rings, whereas electropositive substituents have the opposite effect. For example, (HC)2C=O is the most aromatic (ECRE = 10.3 kcal/mol), and (HC)2C=InH is the most antiaromatic (ECRE = -15.0 kcal/mol). The most refined dissected nucleus-independent chemical shift magnetic aromaticity index, NICS(0)πzz, also agrees with both energetic indexes (R2 = 0.968, for ECRE; R2 = 0.974, for ASE), as do anisotropy of the induced current density plots.
UR - http://www.scopus.com/inward/record.url?scp=78650287059&partnerID=8YFLogxK
U2 - 10.1021/jo1020097
DO - 10.1021/jo1020097
M3 - 文章
AN - SCOPUS:78650287059
SN - 0022-3263
VL - 75
SP - 8252
EP - 8257
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 23
ER -