Unsaturated organic molecules addition compounds with

Addition Compounds of Magnesium with Unsaturated Organic Molecules 105... 

Addition Compounds with Unsaturated Organic Molecules 137... 

Some of the chapters of this book are more focused on the synthetic developments in phosphorus containing materials. This is the case of Chap. 2, which reviews the aspects concerning phosphine acetylenic macrocycles and cages, and Chap. 12, which deals with the important field of P-based cryptands, cyclophanes, and corands. Chapter 4 addresses the potential applications of metal complexes containing anionic phosphoms chains for the synthesis of metal phosphides, whereas the synthesis of P-compounds via the metal catalysed addition of P-H bonds to unsaturated organic molecules is thoroughly reviewed in Chap. 8. 

Certain metal salts can react with unsaturated compounds with the concomitant addition of a solvent molecule or other nucleophile to yield p-substituted metal derivatives. These reactions, called solvometallations or oxymetallations, have a number of applications in organic synthesis. A short treatment of certain classic and important reactions is given here. 

Other organic reactions take place between completely uncharged molecules with no dipole moments. One of the old tests for unsaturation was to treat the compound with bromine water. If the brown colour disappeared, the molecule was unsaturated. We don t use tests like these any more (spectroscopy means we don t need to) but the reaction is still an important one. A simple symmetrical alkene combines with symmetrical bromine in a simple addition reaction. 

The unsaturated character of these trialkyl esters was shown by the ease with which they were attacked by nitric acid, but still more clearly by the formation, with evolution of heat, of stable crystalline addition compounds when they were mixed with cuprous halides. Thus CuC1.P(OC2H5)3 was described as consisting of colourless crystals melting at 190° to 192° C. and soluble in organic solvents.4 This property they share with phosphine, alkylphosphines and phosphorus trihalides. The phosphoric esters were quite indifferent to cuprous halides. Nor were such addition compounds formed either by phosphorous acid itself or by the dialkyl esters, which may show that the latter compounds have the unsymmetrical formula. Phosphorous acid probably exists in both forms, but first as P(OH)3, i.e. when produced from PC13 and Ha0.5 This may be transformed into the unsym-metrieal form through an addition compound HC1.P(0H)3,4 and probably also exists in the form of complex molecules, such as... 

The formation of addition products with ethylene, indicating the unsaturated character of the molecule, would naturally lead to the idea that the structural formula of the compound, in accordance with its relation to ethane and in accordance with our assumption that carbon in organic compounds is tetravalent, should be that of ethane with one valence bond of each carbon atom free and unsatisfied, —CH2—CH2—. 

As an odd-electron molecule, many of the reactions of nitrogen dioxide are typical of free radicals. This applies particularly to its association with atoms such as, H, F, and Cl or other radicals such as, the OH, NO, alkyl, and alkoxy radicals its addition reactions with unsaturated systems such as, olefins, acetylenes, and aromatic compounds, and its hydrogen abstraction reactions. The ability of the NO2 free radical to abstract hydrogen from an organic molecule ... 

Addition and cycloaddition reactions of unsaturated Si=N compounds with organic and inorganic molecules are reported and their crystal structures are presented. 

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