Metal-Oxygen Bonds bonding

The tertiary metal phosphates are of the general formula MPO where M is B, Al, Ga, Fe, Mn, etc. The metal—oxygen bonds of these materials have considerable covalent character. The anhydrous salts are continuous three-dimensional networks analogous to the various polymorphic forms of siHca. Of limited commercial interest are the alurninum, boron, and iron phosphates. Boron phosphate [13308-51 -5] BPO, is produced by heating the reaction product of boric acid and phosphoric acid or by a dding H BO to H PO at room temperature, foUowed by crystallization from a solution containing >48% P205- Boron phosphate has limited use as a catalyst support, in ceramics, and in refractories. 

It is to be expected that tire conduction data for ceramic oxides would follow the same trends as those found in semiconductors, i.e. the more ionic the metal-oxygen bond, the more the oxides behave like insulators or solid elee-trolytes having a large band gap between the valence electrons and holes, and... 

The reduction of a ketone by a metal hydride involves the formation of two bonds the linking of the carbonyl carbon to a hydride and the formation of a metal oxygen bond (4). 

Not many syntheses of phthalocyanines start with phthalimides. This may be due to the oxygen they contain because at elevated temperatures metal-oxygen bonds may be formed with a variety of metals during the synthesis. 

Relative differences between S 2p3/2 and O 1 s ionization potentials show a characteristic separation for oxygen-bound and sulphur-bound sulphoxides. It is clearly shown in Table 20 that sulphur-bound complexes have (O 1 s-S 2p3/2) relative shifts of 365.0 eV, while oxygen-bound complexes have relative shifts of 365.8 eV. Infrared and X-ray crystallographic results also show that most neutral platinum and palladium dialkyl sulphoxide complexes contain metal-sulphur rather than metal-oxygen bonds, while first-row transition metals favour oxygen-bonded sulphoxide. 

To avoid this phase change, zirconia is stabilized in the cubic phase by the addition of a small amount of a divalent or trivalent oxide of cubic symmetry, such as MgO, CaO, or Y2O3. The additive oxide cation enters the crystal lattice and increases the ionic character of the metal-oxygen bonds. The cubic phase is not thermodynamically stable below approximately 1400°C for MgO additions, 1140°C for CaO additions, and below 750°C for Y2O3 additions. However, the diffusion rates for the cations are so low at Xhtstsubsolidus temperatures that the cubic phase can easily be quenched and retained as a metastable phase. Zirconia is commercially applied by thermal spray. It is also readily produced by CVD, mostly on an experimental basis. Its characteristics and properties are summarized in Table 11.8. 

Some inorganic molecules containing metal-oxygen bonds have unusual properties (Scheme 11). In disiloxane, Si-O-Si angles between the single bonds are wider than those of ethers. The bond angle is 144.1° for HjSi-O-SiHj [127] and 111.5° for H3C-O-CH3 [128]. The Si-Si bond distance in the three-membered... 

The oxidation by vanadium(V) of iron(II), a reaction in which a metal-oxygen bond is broken, takes place according to the stoichiometric equation... 

Abstract This review is a summary of supported metal clusters with nearly molecular properties. These clusters are formed hy adsorption or sirnface-mediated synthesis of metal carbonyl clusters, some of which may he decarhonylated with the metal frame essentially intact. The decarhonylated clusters are bonded to oxide or zeolite supports by metal-oxygen bonds, typically with distances of 2.1-2.2 A they are typically not free of ligands other than the support, and on oxide surfaces they are preferentially bonded at defect sites. The catalytic activities of supported metal clusters incorporating only a few atoms are distinct from those of larger particles that may approximate bulk metals. 

When a supported metal on an oxide is prepared from an adsorbed precursor incorporating a noble metal bonded to an oxophilic metal, the result may be small noble metal clusters, each more-or-less nested in a cluster of atoms of the oxophilic metal, which is cationic and anchored to the support through metal-oxygen bonds [44,45]. The simplest such structure is modeled on the basis of EXAFS data as Re4Pt2, made from Re2Pt(CO)i2 (Fig. 6) [45]. 

Figure 19. Variation in dimension of the X-fold cation site in alkali-feldspar for 2+ cations (), obtained by fitting the experimental data of Icenhower and London (1996) for Dca, >sr and Dsa at 0.2 GPa and 650-750°C. In performing the fits was set at 91 GPa for all runs. Error bars are 1 s.d. The positive slope is consistent with measured changes in metal-oxygen bond length from albite to orthoclase (cf Fig. 6). The solid line shows the best-fit linear regression given in Equation (35).

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 above-mentioned results indicate the additive effect of protons. Actually, a catalytic process is formed by protonation of the metal-oxygen bond instead of silylation. 2,6-Lutidine hydrochloride or 2,4,6-collidine hydrochloride serves as a proton source in the Cp2TiCl2-catalyzed pinacol coupling of aromatic aldehydes in the presence of Mn as the stoichiometric reduc-tant [30]. Considering the pKa values, pyridinium hydrochlorides are likely to be an appropriate proton source. Protonation of the titanium-bound oxygen atom permits regeneration of the active catalyst. High diastereoselectivity is attained by this fast protonation. Furthermore, pyridine derivatives can be recovered simply by acid-base extraction or distillation. 

Metal-Oxygen Bond Lengths, M—O—C Angles, and Torsion Angles for Three-Coordinate Aluminum and Gallium Alkoxides and Aryloxides... 

Tethwisch, D.G. and Dumesic, J.A. (1986) Effect of metal-oxygen bond strength on properties of oxides. 1. Infrared spectroscopy of adsorbed carbon monoxide and carbon dioxide, Langmuir, 2, 73. 

Sodium Acetate Complexes of U(VI), Np(VI), Pu(VI) and Am(VI). A Comparison of Metal Oxygen Bond Distance and Bond Force Constant in this Series. Report AECU-3088 (1954). J- chem. Phys. 23, 2105 (1955). 

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