SINGLE TRANSITION-STATE IN THE TRANSFER OF A NEUTRAL PHOSPHORYL GROUP BETWEEN PHENOXIDE ION NUCLEOPHILES IN AQUEOUS-SOLUTION

The second-order rate constants (KArO) for reaction of substituted phenoxide ions with 4-nitrophenyl diphenyl phosphate obey a linear equation over a range of 18 substituents with pKArOH values spanning the pKa of the leaving 4-nitrophenolate ion: log kArO = 0.53pKArOH -6.6. The linear plot is consistent with a mechanism involving a single transition state or a two-step process with a very reactive intermediate with two almost identical transition states for its formation and breakdown; the value of the exponent (0.53) is also not consistent with a regular stepwise process with a discrete intermediate. The symmetrical reaction of 4-nitrophenolate ion with the 4-nitrophenyl ester is slightly imbalanced whereby bond formation does not keep up with bond fission in the transition state; the transition state, therefore, has some phosphorylium ion character. Transfer of the diethylphosphoryl group between weakly basic oxyanion nucleophiles is probably a concerted process with a transition state with more of the character of the pentacoordinate intermediate than it has in the corresponding diphenylphosphoryl group transfer. © 1990, American Chemical Society. All rights reserved.