Theoretical (DFT, GIAO-NMR, NICS) study of carbocations (M+H)+, dications (M2+) and dianions (M2-) from dihydro-dicyclopenta[ef,kl]heptalene (dihydro-azupyrene), dihydro-dicyclohepta[ed,gh]pentalene, and related bridged [14]annulenes.
Theoretical (DFT, GIAO-NMR, NICS) study of carbocations (M+H)+, dications (M2+) and dianions (M2-) from dihydro-dicyclopenta[ef,kl]heptalene (dihydro-azupyrene), dihydro-dicyclohepta[ed,gh]pentalene, and related bridged [14]annulenes.
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二氢-二环戊二烯[ef,kl]庚烯（二氢-azupyrene）、二氢-二环庚烯[ed,gh]的碳阳离子（M H）、二价阳离子（M2）和二价阴离子（M2-）的理论（DFT、GIAO-NMR、NICS）研究
DOI：
10.1039/b412043d
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发表时间：
2005
影响因子：
3.2
通讯作者：
K. Laali
中科院分区：
文献类型：
--
作者：
T. Okazaki;K. Laali
采用密度泛函理论 (DFT) 研究了芘非交替异构体二环戊二烯[ef,kl]庚烯 (azupyrene) (1) 和二环庚烯[ed,gh]pentalene (2) 的二氢和二甲基二氢衍生物（顺式和反式）衍生的质子化的环离子、双电子氧化双阳离子和双电子还原双阴离子。 B3LYP/6-31G(d)、6-31+G(d,p) 或 6-31++G(d,p) 级别。基于规范原子轨道 (GIAO) Deltaδ](13)C 值和自然布居分析 (NPA) 电荷的变化，评估了能量上最有利的环离子以及单重态和三重态二价离子和二价阴离子中的电荷离域模式。通过核无关化学位移 (NICS) 和 DeltaNICS 测量轮烯中的相对芳香性/反芳香性。还通过 DFT 研究了源自双亚甲基和丙二亚基[14]轮烯的单质子化的环离子、双阳离子和双阴离子，以与源自 的顺式二氢异构体进行比较。将计算的 GIAO NMR 数据和优化的几何形状与可用的实验数据进行比较，并将优化的几何形状与 X 射线数据（如果已知）进行比较。还对计算的 GIAO 化学位移进行了基础集依赖性研究。目前的 DFT 工作代表了对源自 和 的二氢衍生物的带电轮烯的首次详细比较理论研究。
The annulenium ions of protonation, the two-electron oxidation dications, and the two-electron reduction dianions derived from dihydro- and dimethyldihydro derivatives (cis and trans) of dicyclopenta[ef,kl]heptalene (azupyrene) (1) and dicyclohepta[ed,gh]pentalene (2), which are the nonalternant isomers of pyrene, were studied by density functional theory (DFT) at the B3LYP/6-31G(d), 6-31+G(d,p), or 6-31++G(d,p) levels. Charge delocalization modes in the energetically most favored annulenium ions, as well as in the singlet and triplet dications and dianions, were assessed based on gauge-including atomic orbital (GIAO) Deltadelta](13)C values and via changes in natural population analysis (NPA) charges. Relative aromaticity/antiaromaticity in the annulenes were gauged via nucleus-independent chemical shift (NICS) and DeltaNICS. Annulenium ions of monoprotonation, the dications, and dianions derived from bismethano- and propanediylidene [14]annulenes were also studied by DFT for comparison with the cis-dihydro isomers derived from . Computed GIAO NMR data and the optimized geometries were compared with the experimental data when available, and the optimized geometries were compared with the X-ray data if known. A basis-set dependency study of the computed GIAO chemical shifts was also undertaken. The present DFT work represents the first detailed comparative theoretical study of charged annulenes derived from the dihydro derivatives of and .
来自甲基化[2.2]偏环芳单烯和[e]-环苯并二甲基二氢芘的新型轮烯双键。
DOI：
10.1021/jo0100594
发表时间：
2001
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Laali,KK;Okazaki,T;Mitchell,RH;Ward,TR
通讯作者：
Ward,TR