ABSTRACT
I. Nucleophilic Activation and Reaction Mechanisms ....................................................... 893
II.
O Isotope Effects........................................................................................................... 895
A. Activation of Water and Associated Equilibrium Isotope Effects.......................... 895
1. Desolvation and H-Bonding.............................................................................. 895
2. Equilibrium Isotope Effects on Hydroxide Formation ..................................... 898
3. Isotope Effects on Coordination of Water by Metal Ions ................................ 898
B. Kinetic Effects on Reactions.................................................................................... 899
1. Experimental and Theoretical Considerations.................................................. 899
2. Nucleophilic Attack on Electrophilic sp
Carbon ............................................ 901
3. Attack on Carbon-Oxygen Double Bonds, Addition
to Carbonyl Compounds ................................................................................... 903
a. Hydrolysis of Formic Acid Derivatives...................................................... 903
b. Carboxypeptidase Catalyzed Amide and Ester Hydrolysis........................ 905
4. Hydrolysis of Phosphate Esters......................................................................... 905
k
Effect on Hexokinase .............................................................................. 907
III.
