APICOPHILICITY AND RING-STRAIN IN FIVE-COORDINATE PHOSPHORANES

Abstract

Abstract In order to dicuss mechanism in organophosphorus chemistry a number of assumptions have to be made. Among them are: (a) that substitutions at tetrahedral phosphorus proceed via five-coordinate intermediates; (b) these intermediates are trigonal bipyramidal; (c) they are formed by apical attack and decompose by apical loss; and (d) if sufficiently long-lived, they may undergo permutational isomerization, that is the ligands may alter their relative dispositions round the phosphorus, before going on to products or back to reactants. Assuming that the course of a given substitution is dictated primarily by thermodynamic considerations, in order to understand the course of that substitution one needs to know how to assess the relative stabilities of the four isomeric tbps (trigonal bipyramids) that can be formed initially and of the others that could be formed by subsequent isomerization, the barriers to those isomerizations, and the relative rates of the various product-forming steps. We have concen...