The use of nuclear magnetic resonance for studying the structures, equilibria, and chemical dynamics of metal chelates is considerably more recent than its application to the study of organic compounds, and the early studies were performed by inorganic chemists rather than those whose interests lie in analytical chemistry. These studies were directed toward the geometrical isomers of metal chelates in the newly and rapidly expanding fields of inorganic chemistry. The initial studies of the aminopolycarboxylates opened up new applications of NMR, which provided a better understanding of the chemistry of metal chelates. The old question of the protonation scheme of these compounds was answered in a quantitative way with exceptional experimental simplicity. The fact that NMR provides a probe not only of molecular dimensions, but also into the behavior of individual metal-ligand bonds, provided a method of classification of the various types of metal-ligand bonding. It is important to observe that these studies were performed using aqueous solutions which is the home of metal-chelate chemistry for analytical applications. Earlier studies were in large part performed with aprotic solvents or solvents of low dielectric constant. The presence of the large solvent water peak was avoided by many researchers. However, much important information is available in the spectral features not blocked by the water peak.