Pseudorotation in pentacoordinated phosphorus compounds. The influence of the conformational transmission effect on the barriers to pseudorotation in cyclic alkoxyphosphoranes

A.E.H. de Keijzer, L.H. Koole, H.M. Buck

Research output: Contribution to journalArticleAcademicpeer-review

17 Citations (Scopus)

Abstract

A variable-temp. 13C NMR study on a series of monocyclic oxyphosphoranes I (R1 = H, Me; R2 = Me, Ph; R3 = Me, OEt; R4 = Me, cyclopentylmethyl, etc.) is used to examine the influence of the conformational transmission effect on the barriers to pseudorotation in pentacoordinated P compds. The pseudorotation rates of monocyclic oxyphosphoranes exhibiting the conformational transmission effect is 2-4 times faster as compared to their counterparts in which the effect is absent. The conformational change in the basal ligands of the intermediate square planar structures, due to the conformational transmission effect, is responsible for the lowering of the activation barriers by 2-3 kJ mol-1.
Original languageEnglish
Pages (from-to)5995-6001
JournalJournal of the American Chemical Society
Volume110
Issue number18
DOIs
Publication statusPublished - 1988

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