Stereomutation of pentavalent compounds: Validating the berry pseudorotation, redressing Ugi's turnstile rotation, and revealing the two- and three-arm turnstiles

Erik P.A. Couzijn, J. Chris Slootweg, Andreas W. Ehlers, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

126 Citations (Scopus)

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 languageEnglish
Pages (from-to)18127-18140
Number of pages14
JournalJournal of the American Chemical Society
Volume132
Issue number51
DOIs
Publication statusPublished - 29 Dec 2010
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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