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.
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