Single transition state in the transfer of a neutral phosphoryl group between phenoxide ion nucleophiles in aqueous solution

Article abstract of DOI:10.1021/ja00178a040

The second-order rate constants (k_Aro) for reaction of substituted phenoxide ions with 4-nitrophenyl diphenyl phosphate obey a linear equation over a range of 18 substituents with pK_ArOH values spanning the pK_a of the leaving 4-nitrophenolate ion: log k_ArO =0.53pK_ArOH -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 dielhylphosphoryl 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.