| Autor: |
Innes, Elizabeth A., Csizmadia, Imre G., Rivail, Jean-Louis, Loos, Michel, Kucsman, Árpád |
| Zdroj: |
Canadian Journal of Chemistry; October 1994, Vol. 72 Issue: 10 p2153-2158, 6p |
| Abstrakt: |
Sulfuranes, containing hypervalent or 10 valence electron central sulfur atoms of the type CH3(H)SCl2(I), H2N(H)SCl2(II), HO(H)SCl2(III), (H2N)2SCl2(IV), and (HO)2SCl2(V) have been studied by abinitioMO computations. All sulfuranes exhibited pseudo trigonal bipyramide structure as appropriate 5 valence electron pairs. The two chlorine atoms were in apical positions and the other two ligands were in equatorial position. The fifth electron pair was a lone pair, also located in an equatorial position. The lone pair "pushed away" the S—Cl bonds from the ideal axis of the trigonal bipyramide and therefore the ClSCl bond angle was always less than 180°. With the changing conformations of the equatorial groups the axial bond lengths are varied. Even though the compounds had constitutionally identical S—Cl bonds at certain torsional angles of the equatory ligands the two S—Cl bond lengths became unequal. The difference between the two bond lengths was used as a measure of the extent of unevenness of the sulfurane structures. This led to the creation and annihilation of certain critical points on the conformational Potential Energy Surfaces. |
| Databáze: |
Supplemental Index |
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