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Stereomutation of pentavalent compounds: validating the Berry pseudorotation, redressing Ugi's turnstile rotation, and revealing the two- and three-arm turnstiles.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2010 Dec 29; Vol. 132 (51), pp. 18127-40. Date of Electronic Publication: 2010 Nov 17. - Publication Year :
- 2010
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Abstract
- A general reaction mechanism describes the qualitative change in chemical topology along the reaction pathway. On the basis of this principle, we present a method to characterize intramolecular substituent permutation in pentavalent compounds. A full description of the geometry around five-coordinate atoms using internal coordinates enables the analysis of the structural changes along the stereomutational intrinsic reaction coordinate. The fluxional behavior of experimentally known pentavalent phosphoranes, silicates, and transition-metal complexes has been investigated by density functional theory calculations, and three principal mechanisms have been identified: Berry pseudorotation, threefold cyclic permutation, and half-twist axial-equatorial interchange. The frequently cited turnstile rotation is shown to be equivalent to the Berry pseudorotation. In combination with graph theory, this approach provides a means to systematically investigate the stereomutation of pentavalent molecules and potentially identify hitherto-unknown mechanisms.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 132
- Issue :
- 51
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 21082808
- Full Text :
- https://doi.org/10.1021/ja105306s