The molecular and electronic structure features of silatranes, germatranes, and their carbon analogsстатья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:Molecular geometries of fifty-six metallatranes N(CH2CH2Y)(3)M-X and fifty-six carbon analogs HC(CH2CH2Y)(3)M-X (M = Si, Ge; X = H, Me, OH, F; Y = CH2, O, NH, NMe, NSiMe3, PH, S) were optimized by the DFT method. Correlations between changes in the bond orbital populations, electron density rho(r), electron density laplacian del(2)rho(r), vertical bar lambda(1)vertical bar/lambda(3) ratio, electronic energy density E(r), bond lengths, and displacement of the central atom from the plane of three equatorial substituents and the nature of substituents X and Y were studied. As the number of electronegative substituents at the central atom increases, the M <- N, M-X, and M-Y bond lengths decrease, while the M <- N bond strength and the electron density at critical points of the M <- N, M-X, and M-Y bonds increase. An increase in electronegativity of a substituent (X or Y) is accompanied by a decrease in the ionicities of the other bonds (M-X, M-Y, and M <- N) formed by the central atom (Si, Ge). A new molecular orbital diagram for bond formation is proposed, which takes into account the interaction of all five substituents at the central atom (M = Si, Ge) in atrane molecules.