Abstract
In most routine applications of NMR only the magnitude of the isotropic average of the coupling constant appears, and this merely as spacings in symmetric multiplet patterns. However, the additional information which comes from the sign of the isotropic average coupling constant and the anisotropy of the coupling tensor is of even greater use as a diagnostic parameter and as an index of the chemical bond. We consider the general empirical patterns in coupling constants which have been very useful in structural applications, taking a global (i.e., entire periodic table) view and giving many examples of each general trend. Because the dependences on structural factors and bond parameters are more easily sorted out in one-bond coupling constants, we have used these to illustrate the dependence on atomic s densities, coordination number, oxidation state, formal hybridization, and electronegativity of substituents on the coupled nuclei, factors which affect the magnitude of coupling constants over any number of bonds. In addition, general trends involving geometric factors (e.g., bond angles) and stereospecificity of one-bond, two-bond, and three-bond couplings are discussed. The theoretical interpretation follows, with a comparative overview of the different computational schemes. Approximate models are used to explain the empirical trends where appropriate. Since a large volume of data has become available for the heavier nuclei, for which relativistic effects cannot be neglected, we quote results of relativistic calculations as well.
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Jameson, C.J. (1987). Spin-Spin Coupling. In: Mason, J. (eds) Multinuclear NMR. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-1783-8_4
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