THE REACTIVITY OF METAL-HYDROXO NUCLEOPHILES AND A RANGE OF BASES IN THE HYDROLYSIS OF THE PHOSPHATE TRIESTER 2,4-DINITROPHENYL DIETHYL PHOSPHATE

The reaction of 16 different nucleophiles with the water-soluble phosp hate triester 2,4-dinitrophenyl diethyl phosphate (1 = DNPDEP) has bee n studied at 35 degrees C and I = 0.1 mol dm(-3) (KNO3). The nucleophi les studied included a number of metal-hydroxo complexes, such as [M(N H3)(5)OH](2+) (M = Co-III, Cr-III), the macrocyclic complexes [Zn(CR)O H](+), [Co([15]aneN(5))OH](2+), and the hydroxoaqua complex [Cu (tmen) (OH)(OH2)](+)(tmen = N,N,N',N'-tetramethylethylenediamine). The Brons ted plot of log k(N) versus pK(a) shows good linearity with a slope be ta of 0.39. The monohydroxo complexes lie on the line, but the hydroxo -aqua complex shows enhanced reactivity due to intramolecular hydrolys is taking place. Published by Elsevier Science Ltd.