By Prof. Dr. Edwin C. Constable(auth.)
This publication is a hugely readable creation to the reactions of coordinated ligands, that have turn into a useful gizmo in natural synthesis. Bridging the space among the conventional fields, this article offers the elemental suggestions of ligand reactivity in addition to man made functions of those reactions.
themes coated include
* ideas of metal-ligand interplay * Reactions of coordinated ligands with nucleophiles and electrophiles * Oxidation and aid of coordinated ligands * Cyclic and encapsulating ligands, template influence and supramolecular chemistry
rigorously chosen examples, lucidly designed figures and schemes in addition to various learn difficulties make this e-book an amazing consultant for college kids and practitioners of natural synthesis. References to additional analyzing also are integrated.
Chapter 1 advent (pages 1–21):
Chapter 2 The Metal?Ligand interplay (pages 22–45):
Chapter three Reactions of Co?Ordinated Carbonyl Compounds with Nucleophiles (pages 46–62):
Chapter four different Reactions of Co?Ordinated Ligands with Nucleophiles (pages 63–88):
Chapter five Stabilisation of Anions and the Reactions of Co?Ordinated Ligands with Electrophiles (pages 89–134):
Chapter 6 Cyclic Ligands and the Template impression (pages 135–182):
Chapter 7 The Three?Dimensional Template influence, Supramolecular Chemistry and Molecular Topology (pages 183–232):
Chapter eight Reactions of fragrant and Heterocyclic Ligands (pages 233–262):
Chapter nine Oxidation and aid of Co?Ordinated Ligands (pages 263–287):
Chapter 10 Envoi (pages 288–299):
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Additional info for Metals and Ligand Reactivity: An Introduction to the Organic Chemistry of Metal Complexes, New, revised and expanded edition
The covalent representation places a single positive charge on each of the water oxygen atoms and a —3 charge on the chromium centre (Fig. 2-13). The 'truth' lies somewhere between these two extremes, and the assessment of covalent and ionic contributions to bonding has attracted considerable attention. Pauling devised the electroneutrality principle and suggested that the relative importance of ionic and covalent components was such that the overall charge on any one atom did not exceed ±1. In the context of the [Cr(H2O)6]3+ ion, this leads to a description in which the metal centre is neutral and each oxygen bears a charge of + \.
In this case, the metal may serve a dual role in activating the electrophilic site and in increasing the leaving group ability of the outgoing ion. This is seen in the mercurymediated transesterificaton reactions of thioesters. A common synthetic application is seen in Fig. 2-23, where mercury(n) is used to remove a protecting group. The interaction of the mercury(n) with the sulfur atom enhances the leaving ability of the SR group, and increases the rate by many orders of magnitude. The well-known action of silver(i) salts on nucleophilic substitution in alkyl halides is another commonplace example of this effect.
A more subtle effect of π-bonding is seen in ruthenium complexes of pyrazine. We saw in Fig. 2-20 that co-ordination of a pyrazinium cation to a ruthenium(m) centre resulted in an increase in its acidity. However, co-ordination to a ruthenium(n) centre results in a decrease in acidity. 6 Figure 2-30. Competing polarisation and back-bonding effects control the acidity of a pyrazinium cation co-ordinated to ruthenium(n) 44 2 The Metal-Ligand Interaction donation. 6. We see in Fig. 2-30 the true competition between the polarisation and π-bonding effects.
Metals and Ligand Reactivity: An Introduction to the Organic Chemistry of Metal Complexes, New, revised and expanded edition by Prof. Dr. Edwin C. Constable(auth.)