Reaction of coordinated

P. S. Braterman, Reactions of Coordinated Eigands, Plenum Press, New York Vol. 1, 1986, iacludes over 1000 pages of carboa boaded ligand reactions, essentially organometaUic and carbonyls Vol. 2, 1989, discusses noncarbon bonded ligands. 

A related example is the reaction of NbCls and thf with (Me3Si)2NN(SiMe3)2 in CH2CI2 to give an 80% yield of [(/Lt-N2) NbCl3(th02 2]- Occasionally an N=N triple bond can be formed within a metal complex, e.g. by reaction of coordinated NH3 with HNO2, but this method is of limited application, e.g. ... 

The chemical reactivity of coordinated N2 has been extensively studied because of its potential relevance to the catalytic and biological fixation of N2 to NH3 (p. 1035). For other recent work on the reactions of coordinated dinitrogen see refs. 41-44... 

This book is a highly readable introduction to the reactions of coordinated ligands. Bridging the gap between the traditional fields, this text presents the basic concepts of ligand reactivity as well as many synthetic applications of these reactions. 

It is apparent, from the above short survey, that kinetic studies have been restricted to the decomposition of a relatively few coordination compounds and some are largely qualitative or semi-quantitative in character. Estimations of thermal stabilities, or sometimes the relative stabilities within sequences of related salts, are often made for consideration within a wider context of the structures and/or properties of coordination compounds. However, it cannot be expected that the uncritical acceptance of such parameters as the decomposition temperature, the activation energy, and/or the reaction enthalpy will necessarily give information of fundamental significance. There is always uncertainty in the reliability of kinetic information obtained from non-isothermal measurements. Concepts derived from studies of homogeneous reactions of coordination compounds have often been transferred, sometimes without examination of possible implications, to the interpretation of heterogeneous behaviour. Important characteristic features of heterogeneous rate processes, such as the influence of defects and other types of imperfection, have not been accorded sufficient attention. 

Mechanistic aspects of the photochemical reactions of coordination compounds. M. S. Wrighton, Top. Curr. Chem., 1976, 65, 38-104 (196). 

Lewis Acid Catalysis and the Reactions of Coordinated Ligands... 

A large amount of the work on palladium isocyanide complexes has been mentioned earlier, in discussions on insertion reactions 30,74,108,169,170) and on addition reactions of coordinated isocyanides 25, 33, 34, 49) the reactions of [Pd(CNBu )2] with oxygen 107) and with various olefins 29, 110) were noted. 

Minghetti, G., Bonati, F. and Banditelli, G. (1976) Carhene Complexes Of Gold (III) And Reactions Of Coordinated Ligand. Inorganic Chemistry, 15(7), 1718-1720. 

It is salutary to read the comment, At the time when I became interested in the reactions of coordination compounds the formula of not a single aquo complex was known with certainty, made by Taube in a recent review (364). In marked contrast, this review is predominantly concerned with the intimate detail of the mechanisms of sol-... 

Wrighton, M. S. Mechanistic Aspects of the Photochemical Reactions of Coordination Compounds. 65,37-102 (1976). 

O Brien, P. (1983). Polyhedron 2, 223. An excellent review of racemization reactions of coordination compounds in the solid state. 

Reactions such as this are electrophilic substitutions, and other electrophiles such as N02 , Cl l3CO, or Cl IO can be substituted on the rings without destroying the complex. Such chemical behavior illustrates the extreme stability of complexes of this type. It is apparent that the nature of the bonding in the chelate rings is as important as is their size. Other reactions of coordinated ligands will be shown in later chapters. 

In this chapter, a survey of the enormously broad area of reactions of coordination compounds will be presented, and some of the basic mechanisms of the reactions will be presented. However, reactions of coordination compounds is such a very broad area that this chapter (as would be the case of any chapter) can present only the basic concepts and an elementary introduction to the field. More detailed coverage will be found in the references listed at the end of the chapter. The classic books in the field are Basolo and Pearson (1974) and Wilkins (1991), which present excellent and detailed reviews of the literature. We begin the chapter by illustrating some of the synthetic methods that have been useful for synthesizing coordination compounds. 

The replacement of one ligand by another is the most common type of reaction of coordination compounds, and the number of reactions of this type is enormous. Some are carried out in aqueous solutions, some in nonaqueous media, and others can be carried out in the gas phase. One such reaction is... 

As in many areas of chemistry, there are reactions of coordination compounds that are not what they appear. For example, the reaction... 

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