The effect of the valent state of the heteroatom on the spectrochemical evidence of conjugation in allyl compounds of sulfur and phosphorus
| العنوان: | The effect of the valent state of the heteroatom on the spectrochemical evidence of conjugation in allyl compounds of sulfur and phosphorus |
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| المؤلفون: | P. P. Shorygin, A. N. Isaev |
| المصدر: | Russian Chemical Bulletin. 44:37-41 |
| بيانات النشر: | Springer Science and Business Media LLC, 1995. |
| سنة النشر: | 1995 |
| مصطلحات موضوعية: | Crystallography, Chemistry, Absorption band, Computational chemistry, Heteroatom, Bathochromic shift, Hypervalent molecule, Allyl compound, Molecule, Molecular orbital, General Chemistry, Ionization energy |
| الوصف: | The effect of valency of the heteroatom on the spectrochemical evidence of the conjugation in allyl derivatives of SII,VI and PIII,IV was studied by quantum chemical methods. The geometric and electronic structures of thetrans- andgauche-conformers, including those for allyl compounds of PV with equatorial or axial P-C bonds, were calculated. According to the calculations, inversion of the higher occupied molecular orbitals (MO) and the convergence of their energies resulting from the replacement of weak n,π-conjugation by strong π,σ-conjugation should occur on going from SII and PIII to SVI and PV. Increasing the interaction between the higher occupied MO of the fragments in the non-planar conformation of the molecule causes strengthening of the spectral evidence of conjugation: a decrease in the first ionization potential and a bathochromic shift of the long-wavelength absorption band in the electronic spectrum. The increased relative stability of thegauche-conformers of allyl compounds of hypervalent elements was explained by the through-space interaction between the vacant d-orbitals of the SVI and PV atoms and the π-orbital of the C=C bond. Charge transfer between the molecular fragments makes the major contribution to the energy of conjugation. |
| تدمد: | 1573-9171 1066-5285 |
| DOI: | 10.1007/bf00696954 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::14358041e8ac9b9e5a56987b41299ed9 https://doi.org/10.1007/bf00696954 |
| Rights: | CLOSED |
| رقم الانضمام: | edsair.doi...........14358041e8ac9b9e5a56987b41299ed9 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15739171 10665285 |
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| DOI: | 10.1007/bf00696954 |