Metal nitrogen—oxygen bonds

Into Metal-Nitrogen, -Oxygen, and - Sulfur Bonds... 

A few final comments should be made on the insertions of substrates containing C-C multiple bonds into the bonds between a transition metal and an electronegative heteroatom. First, insertions of olefins into related thiolate and phosphide complexes are as rare as insertions into alkoxo and amido complexes. Reactions of acrylonitrile into the metal-phosphorus bonds of palladium- and platinum-phosphido complexes to give products from formal insertions have been observed, and one example is showm in Equation 9.90. However, these reactions are more likely to occur by direct attack of the phosphorus on the electrophilic carbon of acrylonitrile than by migratory insertion. Second, the insertions of alkynes into metal-oxygen or metal-nitrogen covalent bonds are rare, even though the C-C ir-bond in an alkyne is weaker than the ir-bond in an alkene. 

Nitriles. Nitriles can be prepared by a number of methods, including ( /) the reaction of alkyl haHdes with alkaH metal cyanides, (2) addition of hydrogen cyanide to a carbon—carbon, carbon—oxygen, or carbon—nitrogen multiple bond, (2) reaction of hydrogen cyanide with a carboxyHc acid over a dehydration catalyst, and (4) ammoxidation of hydrocarbons containing an activated methyl group. For reviews on the preparation of nitriles see references 14 and 15. 

While metal-nitrogen and metal-oxygen bonded compounds dominate nucleobase coordination chemistry, examples in which metal-carbon bonds are formed have been identified. Early studies on the synthesis of metal-labeled DNA demonstrated that nucleotide-triphosphates, UTP, CTP, dUTP, and dCTP, can undergo mercury modification at C5 (82,83). The UTP derivative was also shown to act as a substrate for RNA polymerase in the presence of mercaptans (83). Later, guano-sine was shown to undergo mercury modification at C8 though, in this case, the purine was multiply substituted, 21 (84). 

The sodium and calcium salts of EDTA (ethylenediaminetetraacetic acid, Fig. 9.3.1.) are common sequestrants in food products. A three-dimensional representation of EDTA is shown in color Fig. 9.3.2. The EDTA ion is an especially effective sequestrant, forming up to six coordinate covalent bonds with a metal ion. These bonds are so named because a lone pair of electrons on a single atom serves as the source of the shared electrons in the bond between the metal ion and EDTA. The two nitrogen atoms in the amino groups and the oxygen... 

In this chapter and in Chapters 10-12, we will review and validate some methods for asymmetric (transfer) hydrogenation of carbon-oxygen and carbon-carbon double bonds catalysed by non-metallic systems, homogeneous transition metal catalysts and biocatalysts. Reduction of carbon-nitrogen double bond systems will be reported in another volume of this series. 

The result is that for minimum activation energy, the bond YZ must be stretched and weakened before the final bond XY is established. Quantitative calculations show that the activation energy evaluated in this manner amounts, at the most, to 7 % of the bond energy YZ. In accordance with this theory, recombinations of atoms of hydrogen, nitrogen, oxygen, chlorine on metal surfaces... 

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