Reactions of co-ordinated

A full discussion of the reactions of molecular oxygen involved in dioxygen adducts would require a separate review. Moreover, the reactions of co-ordinated molecular oxygen are discussed elsewhere l-8) dioxygen adducts of biological systems (7) and synthetic group VIII metal complexes 1,3) being of particular interest. 

Reactions of Co-ordinated CO and Lewis Acid Adducts. The details of the preparation and properties of [Me3SiFe(COSiMe3XCO)3]2 (see Vol. 1, p. 139) have been published.The reaction of FeiCO) and MeC H N=PPh, in THF yields [Fe(CO)4(CNCftH4Me)], [Fe(CO)3(CNC6H4Me2], and Ph3PO (o-, m-, and p-isomers all isolated ). This is a rare example of deoxygenation of co-ordinated CO without M—C bond cleavage. The p-Me complexes can also be obtained from the reaction of Fe2(CO)g and p-MeC H N PPhj in benzene at room temperature. 

Reactions of Co-ordinated CO. Following the reports cited in Volume 1 (p. 168) of silyl-ether type metal carbonyls, a further example has been reported. Thus excess Co2(CO)g reacts with R2SiH2 (R = Ph or Et) to give the complex [R2SiCo4(CO)i4]. On the basis of i.r. and mass spectral evidence structure (64) is proposed. Co2(CO)g also reacts with ClgBNEtg in a 7 9 mole ratio... 

PS. Braterman, Reactions of Co-ordinated Ligands, Vol. 2, Plenum, New York, 1989. 

Reactions of Co-ordinated Carbonyl Compounds with Nucleophiles... 

In conclusion, the hydrolytic and other reactions of co-ordinated amino acid derivatives with nucleophiles may proceed by two major routes. The first involves a moderate acceleration by general acid catalysis of a monodentate TV-bonded ligand, whilst the second may involve very dramatic rate increases (by a factor of a million or so) associated with didentate chelating TV O-bonded ligands. There is little evidence for the widespread involvement of co-ordinated nucleophiles attacking the carbonyl in amino acid derivatives, although some special, and well characterised, examples with cobalt(m) complexes are considered in the next chapter. 

In the next chapter we will observe further reactions of co-ordinated carbonyl compounds in which the nucleophile is also co-ordinated to the metal centre. These intramolecular reactions are sufficiently different in character to merit separate treatment. 

In this book we are not concerned with organometallic reactivity of compounds containing M-C bonds, and so to all intents and purposes this section is about the reactions of nitriles or cyanides with nucleophiles. Reactions of co-ordinated alkynes are adequately discussed elsewhere. 

An article about the reactions of co-ordinated nitrile ligands... 

A short review dealing with reactions of co-ordinated nitriles... 

Stabilisation of Anions and the Reactions of Co-ordinated Ligands with Electrophiles... 

In the same way that the formation of the enolate may be promoted by co-ordination to a metal ion, so may the reactions of that enolate be promoted or modified. Spectacular examples of the reactions of co-ordinated enolates are observed in the electrophilic halo-genation of /3-ketoesters. These reactions are accelerated dramatically in the presence of copper(n) and other metal ions (Fig. 5-6). 

However, the reactions of co-ordinated 1,3-dicarbonyl complexes with electrophiles are not always so simple. The reaction of dicyanogen with co-ordinated, and free, 1,3-diketonates has been studied in some detail and results in the formation of a variety of exotic products, such as 5.1, 5.2 and 5.3. 

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