By Edwin C. Constable
This booklet is a hugely readable creation to the reactions of coordinated ligands, that have develop into a useful gizmo in natural synthesis. Bridging the space among the conventional fields, this article provides the elemental thoughts of ligand reactivity in addition to artificial functions of those reactions. issues coated comprise * rules of metal-ligand interplay * Reactions of coordinated ligands with nucleophiles and electrophiles * Oxidation and aid of coordinated ligands * Cyclic and encapsulating ligands, template impact and supramolecular chemistry rigorously chosen examples, lucidly designed figures and schemes in addition to quite a few examine difficulties make this e-book a terrific advisor for college students and practitioners of natural synthesis. References to extra analyzing also are integrated.
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Extra info for Metals and Ligard Reactivity: An Introduction to the Organic Chemistry of Metal Complexes
If a polydentate ligand binds to a single metal atom by two or more donor atoms, the resultant complex is known as a chelate (Greek chelos, claw). Such chelated complexes are kinetically and thermodynamically more stable, with respect to ligand displacement, than comparable compounds with an equal number of equivalent monodentate ligands. What are the steric consequences of chelation? 26 2 The Metal-Ligand Interaction Μ Figure 2-3. The sequential formation of metal-ligand bonds in a chelated complex.
The result is that the lone pair becomes 'less' available to the donor atom; thus any properties of the ligand associated with the presence of the lone pair will be modified. The simplest way in which this might be expressed is in the nucleophilicity of the donor atom. As an example, the nucleophilicity of amines is associated with the possession of a lone pair of electrons on the nitrogen atom; upon co-ordination, these electrons are involved in the metal-nitrogen bond, and one would expect the nucleophilic properties to be reduced, or to disappear entirely.
However, forms such as Λ λλλ and Λ λλδ, which differ in the arrangement of only one chelate ring, are related as diastereomers, and are expected to possess different conformational energies and associated chemistry. The origin of the differing chemical properties of the various diastereomers is most easily seen by considering a square planar complex which has only two en ligands. This could exist as λλ, δδ or λδ diastereomers, with the λλ and δδ forms related as an enantiomeric pair.
Metals and Ligard Reactivity: An Introduction to the Organic Chemistry of Metal Complexes by Edwin C. Constable