By Prof. Dr. Edwin C. Constable(auth.)
This e-book is a hugely readable creation to the reactions of coordinated ligands, that have turn into a useful gizmo in natural synthesis. Bridging the distance among the normal fields, this article offers the elemental strategies of ligand reactivity in addition to artificial functions of those reactions.
subject matters lined include
* rules of metal-ligand interplay * Reactions of coordinated ligands with nucleophiles and electrophiles * Oxidation and relief of coordinated ligands * Cyclic and encapsulating ligands, template impression and supramolecular chemistry
conscientiously chosen examples, lucidly designed figures and schemes in addition to a variety of examine difficulties make this publication an incredible advisor for college students and practitioners of natural synthesis. References to additional studying also are incorporated.
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 impact (pages 135–182):
Chapter 7 The Three?Dimensional Template impression, Supramolecular Chemistry and Molecular Topology (pages 183–232):
Chapter eight Reactions of fragrant and Heterocyclic Ligands (pages 233–262):
Chapter nine Oxidation and relief of Co?Ordinated Ligands (pages 263–287):
Chapter 10 Envoi (pages 288–299):
Read or Download Metals and Ligand Reactivity: An Introduction to the Organic Chemistry of Metal Complexes, New, revised and expanded edition PDF
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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
There are a number of π-bonding interactions which we will encounter in co-ordination complexes. As far as the metal ion is concerned, the d and/? orbitals are suitable for π-bonding; these may be either full or empty (Fig. 2-25). If the ligand possesses a π-bonding system, then its existing π- or K*-orbitals may be of the correct symmetry for overlap with metal ρ or d orbitals. Furthermore, any other M-d L-π* M-p L-π* Figure 2-25. The interaction of metal d or metal/? orbitals with the 7i*-levels of a ligand such as carbon monoxide or an imine.
The polarisation of the ligand resulting from co-ordination to a metal can be reflected in the ground state properties of the ligand, as discussed above. How may changes in the ligand polarisation be detected by other molecules in the immediate environment? Consider a ligand co-ordinated to a positively charged metal ion. We expect to see the build-up of positive charge on the ligand. This will result in an enhanced electrostatic interaction between the ligand and any negatively charged or dipolar molecules in the environment.
6. We see in Fig. 2-30 the true competition between the polarisation and π-bonding effects. Even though the ruthenium(n) complex is positively charged, the π-bonding interaction is sufficient to reverse the expected increased pKa resulting from polarisation. 5 Conclusions In this chapter we have seen the three ways in which co-ordination to a metal ion may modify the properties of a ligand. In any real metal-ligand system, the observed reactivity is expected to be a subtle blend of all three. In the remainder of this book we will consider the ways in which these various effects work in real complexes.
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.)