The phosphate monoester in 2-H is hydrolyzed an unprecedented 10(11) times more rapidly than the corresponding unbound phosphate. Clean conversion of the bidentate monoester (2-H) to the tridentate inorganic phosphate (3), together with the crystal structure of an analog of 2-H, provides detailed mechanistic insight into the hydrolysis reaction. [GRAPHICS] gradients for coherence-transfer selection in combination with H-1 detection is a powerful method for obtaining two- and three-bond H-1-C-13 connectivities between hyperfine-shifted resonances.