Trinuclear approach to hydrolyzing a phosphate diester

Structure and Reactivity of Dinuclear Cobalt(III) Complexes with Peroxide and Phosphate Diester Analogues Bridging the Metal Ions

“…In general, phosphonate monoesters are about as stable as phosphate diesters. The second-order rate contant for hydroxide-catalyzed hydrolysis of bis( p -nitrophenyl) phosphate, p -nitrophenyl phenylphosphonate, and p -nitrophenyl methyl phosphonate at 25 °C are 2.0 × 10 -5 , 8.3 × 10 -5 , and 2.8 × 10 -5 M -1 s -1 , respectively . Assuming that the second-order rate constant for hydroxide-catalyzed hydrolysis of methyl phenyl phosphonate is comparable to that for the hydrolysis of dimethyl phosphate (6.8 × 10 -12 M -1 s -1 ), the pseudo-first-order rate constant for hydroxide-catalyzed hydrolysis of the monoester at pH 7 should be ∼10 -18 s -1 .…”