Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation
Identifieur interne : 001959 ( Main/Exploration ); précédent : 001958; suivant : 001960Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation
Auteurs : A. B. Rozhenko [Allemagne] ; W. W. Schoeller [Allemagne] ; M. I. Povolotskii [Ukraine]Source :
- Journal of Molecular Structure: THEOCHEM [ 0166-1280 ] ; 2000.
English descriptors
- KwdEn :
- Teeft :
- Bond length, Bond length variation, Bond lengths, Bond order, Bond orders, Butadiene, Chem, Chemical shielding, Chemical shielding values, Chemical shift calculations, Chemical shift values, Chemical shifts, Conformation, Conjugation, Conjugation effects, Delocalization, Dihedral, Dihedral angle, Dihedral angles, Double bond, Energy balances, Gauche, Gauche structure, Geometrical parameters, Geometry optimization, H3si, H3si groups, Initio calculations, Interatomic, Interatomic angles, Interatomic distances, Isodesmic reactions, Khim, Moiety, Molecular structure, Natural charges, Optimized, Optimized structures, Orthogonal, Orthogonal conformation, Phosphorus, Phys, Povolotskii, Relative energies, Romanenko, Rotational, Rotational energy surface, Rotational energy surfaces, Rozhenko, Single bond distances, Tetrahedron lett, Theochem, Trans, Transition state, Transition states, Wiberg, Wiberg bond indices, Wiberg indices.
Abstract
Abstract: The 2,3-diphospha- and 2-aza-3-phosphabuta-1,3-dienes (H3Si)2CP–XCYY′ (1 X=P, Y,Y′=NH2; 2 X=P, Y,Y′=H; 7 X=N, Y,Y′=NH2; 8 X=N, Y,Y′=H; 9 X=N, Y=NH2 (E-), Y′=H (Z-); 10 X=N, Y=H (E-), Y′=NH2 (Z-)) as well as the isostructural butadienes (H3Si)2CCH–CHCY2 (5 Y=NH2; 6 Y=H), the symmetrical diphosphabutadienes (H3Si)2CP–PC(SiH3)2 (3) and (H2N)2CP–PC(NH2)2 (4), were explored with ab initio calculations. The analysis of the geometrical parameters, natural atomic charges and Wiberg bond indices, rotational energy surfaces and energies of the isodesmic reactions shows an essential contribution of π-electron delocalization for the model butadienes 1, 5, 7, 9, and 10. On the contrary, in 2, 3 and 4 the stabilization due to the conjugation effects is negligible or in general absent. The NMR chemical shielding values, calculated for 1–10 with the GIAO procedure at the RHF/6-311+G(d,p) level, as well as those published for the electron-rich butadienes (Me3Si)2CP–XC(NMe2)2 (X=N,P), agree qualitatively with the global conception of variation of the structural parameters and charge distribution due to the π-electron delocalization in the molecules.
Url:
DOI: 10.1016/S0166-1280(99)00206-7
Affiliations:
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The analysis of the geometrical parameters, natural atomic charges and Wiberg bond indices, rotational energy surfaces and energies of the isodesmic reactions shows an essential contribution of π-electron delocalization for the model butadienes 1, 5, 7, 9, and 10. On the contrary, in 2, 3 and 4 the stabilization due to the conjugation effects is negligible or in general absent. The NMR chemical shielding values, calculated for 1–10 with the GIAO procedure at the RHF/6-311+G(d,p) level, as well as those published for the electron-rich butadienes (Me3Si)2CP–XC(NMe2)2 (X=N,P), agree qualitatively with the global conception of variation of the structural parameters and charge distribution due to the π-electron delocalization in the molecules.</div></front></TEI><affiliations><list><country><li>Allemagne</li><li>Ukraine</li></country></list><tree><country name="Allemagne"><noRegion><name sortKey="Rozhenko, A B" sort="Rozhenko, A B" uniqKey="Rozhenko A" first="A. B." last="Rozhenko">A. B. Rozhenko</name></noRegion><name sortKey="Schoeller, W W" sort="Schoeller, W W" uniqKey="Schoeller W" first="W. W." last="Schoeller">W. W. Schoeller</name></country><country name="Ukraine"><noRegion><name sortKey="Povolotskii, M I" sort="Povolotskii, M I" uniqKey="Povolotskii M" first="M. I." last="Povolotskii">M. I. Povolotskii</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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