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.
Original language | English |
---|---|
Pages (from-to) | 18127-18140 |
Number of pages | 14 |
Journal | Journal of the American Chemical Society |
Volume | 132 |
Issue number | 51 |
DOIs | |
Publication status | Published - 29 Dec 2010 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry