What can the geometry tell about the charge distribution in the mesoionic heterocycles? A DFT study on the SCN 4 R 2 system
This computational organic chemistry study was performed using the hybrid functional B3LYP. Many basis sets were evaluated and the basis set 6‐31G(d) was found to be the most practical in terms of time and accuracy. The study presents the first method in the chemical literature that allows estimatio...
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| Published in | Journal of physical organic chemistry Vol. 23; no. 1; pp. 67 - 74 |
|---|---|
| Main Author | |
| Format | Journal Article |
| Language | English |
| Published |
01.01.2010
|
| Online Access | Get full text |
| ISSN | 0894-3230 1099-1395 |
| DOI | 10.1002/poc.1586 |
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| Abstract | This computational organic chemistry study was performed using the hybrid functional B3LYP. Many basis sets were evaluated and the basis set 6‐31G(d) was found to be the most practical in terms of time and accuracy. The study presents the first method in the chemical literature that allows estimation of submolecular charges in mesoionic compounds. The theory was built on a reference model structure for which the absolute value of charge of the aromatic
p
‐orbitals is known. This is the cornerstone, and by employing the harmonic oscillator model of aromaticity (HOMA) many parameters can be quantified. The electronic structure of the title compound was the subject of this approach. The study addressed the following points: geometries, infrared frequencies, NMR chemical shifts, calculated charges, a chemical reactivity, and the frontier orbitals. The calculations illustrate that the
π
‐system of the CN
4
segment includes considerable aromatic character and carries a positive charge while the overall charge is negative. This allows classifying it as a
σ
‐acceptor/
π
‐donor while the exocyclic counter anion, the sulfur atom, is a
σ
‐donor/
π
‐acceptor. The substituents (R groups) in this case are only
σ
‐donors. The approach may be applied to other mesoionic and mesoaromatic systems. Copyright © 2009 John Wiley & Sons, Ltd. |
|---|---|
| AbstractList | This computational organic chemistry study was performed using the hybrid functional B3LYP. Many basis sets were evaluated and the basis set 6‐31G(d) was found to be the most practical in terms of time and accuracy. The study presents the first method in the chemical literature that allows estimation of submolecular charges in mesoionic compounds. The theory was built on a reference model structure for which the absolute value of charge of the aromatic
p
‐orbitals is known. This is the cornerstone, and by employing the harmonic oscillator model of aromaticity (HOMA) many parameters can be quantified. The electronic structure of the title compound was the subject of this approach. The study addressed the following points: geometries, infrared frequencies, NMR chemical shifts, calculated charges, a chemical reactivity, and the frontier orbitals. The calculations illustrate that the
π
‐system of the CN
4
segment includes considerable aromatic character and carries a positive charge while the overall charge is negative. This allows classifying it as a
σ
‐acceptor/
π
‐donor while the exocyclic counter anion, the sulfur atom, is a
σ
‐donor/
π
‐acceptor. The substituents (R groups) in this case are only
σ
‐donors. The approach may be applied to other mesoionic and mesoaromatic systems. Copyright © 2009 John Wiley & Sons, Ltd. |
| Author | Irshaidat, Tareq |
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| Cites_doi | 10.1055/s-2003-44357 10.1021/ci00011a011 10.1016/0009-2614(82)80012-2 10.1021/jo0504767 10.1103/PhysRevB.37.785 10.1016/S0040-4039(98)00069-0 10.1063/1.1677527 10.1016/0013-4686(95)00207-U 10.1021/ja00204a001 10.1063/1.1740588 10.1021/cr990326u 10.1063/1.1480445 10.1021/ja01485a033 10.1063/1.449486 10.1063/1.1732476 10.1063/1.448799 10.1063/1.462066 10.1016/0040-4020(82)80186-5 10.1002/jcc.540110311 10.1021/jp000156l 10.1063/1.438980 10.1016/S0040-4039(01)94175-9 10.1063/1.464913 10.1021/ja00179a005 10.1063/1.456153 10.1016/j.tetlet.2005.02.084 10.1021/cr00088a005 10.1021/jp0104839 |
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| References | e_1_2_6_31_2 Yelamaggad C. V (e_1_2_6_2_2) 1993; 32 e_1_2_6_18_2 e_1_2_6_19_2 e_1_2_6_12_2 e_1_2_6_13_2 e_1_2_6_10_2 e_1_2_6_11_2 e_1_2_6_32_2 e_1_2_6_16_2 Scrosati B (e_1_2_6_30_2) 1993 e_1_2_6_17_2 e_1_2_6_14_2 e_1_2_6_15_2 e_1_2_6_20_2 e_1_2_6_8_2 e_1_2_6_7_2 e_1_2_6_9_2 e_1_2_6_29_2 e_1_2_6_4_2 e_1_2_6_3_2 e_1_2_6_6_2 e_1_2_6_5_2 e_1_2_6_24_2 e_1_2_6_23_2 e_1_2_6_22_2 e_1_2_6_21_2 e_1_2_6_28_2 e_1_2_6_27_2 e_1_2_6_26_2 e_1_2_6_25_2 |
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| Title | What can the geometry tell about the charge distribution in the mesoionic heterocycles? A DFT study on the SCN 4 R 2 system |
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