Clusters oxide/hydroxide complexes

Trivalent Chemistry Cyclopentadienyl Rare Earth Metal Cluster Complexes Lanthanide Oxide/Hydroxide Complexes Oxide and Sulfide Nanomaterials Near-Infrared Materials. 

Lanthanides in Living Systems Lanthanides Coordination Chemistry Lanthanides Luminescence Applications Lmninescence Lanthanides Magnetic Resonance Imaging Lanthanide Oxide/Hydroxide Complexes Carboxylate Lanthanide Complexes with Multidentate Ligands Rare Earth Metal Cluster Complexes Supramolecular Chemistry from Sensors and Imaging Agents to Functional Mononuclear and Polynuclear Self-Assembly Lanthanide Complexes. 

In very acidic solutions, bismuth(III) exists in the form of the nonaaquo ion [Bi(H20)9] +, which is similar to the aquo complexes of the lanthanide ions, but partial hydrolysis of bismuth(III) salts leads to the formation of bismuth oxo clusters. The core structure of these complexes is often based upon a Bie octahedral core with oxide, hydroxide, or alkoxide functions bridging the edges and/or faces of the octahedron. The [Bi6(OH)i2] + ion (11) has been studied spectroscopically. In oxo clusters, the octahedron is face-bridged by eight oxo or alkoxide functions (12). Such core structures have been found in the hydrolysis of bismuth nitrate or perchlorate. ... 

Next, (1) CO binds to Cluster C to yield a Credi-CO complex (2) CO undergoes attack by the metal-bound hydroxide and is oxidized to CO2 as Cluster C is reduced by two electrons to the Cred2 state (3) CO2 is released and a second CO molecule binds to Cluster C to form a Cred2-CO complex (4) electrons are transferred from Cred2-CO to reduce Cluster B as the second molecule of CO2 is released. This mecha-... 

For low selenosulphate concentrations, only the small crystals were formed, even in thicker films, and this was rationalized by the lower steady-state selenide concentration, which would favor cluster growth over ion-by-ion formation (the product of free lead and selenide ions needs to be larger than the solubility product of PbSe for ion-by-ion deposition to occur). An important difference between the citrate depositions and the NTA or hydroxide ones is that, even in the ion-by-ion citrate deposition, some low concentration of colloidal hydrated oxide was present, due to the relatively low complexing strength of citrate. The pH of the hydroxide baths (> 13) was much higher than that of the citrate or NT A baths (10.8). 

In the report that described the synthesis of 108 (777), Whitmire also observed that the reaction between NaBi03 and methanolic [Fe(CO)s] in the presence of hydroxide afforded the trianionic species [Bi Fe(CO)4 4]3, 110, which was subsequently characterized by X-ray crystallography (775). Cluster 110 contains a central bismuth atom tetrahedrally coordinated by four Fe(CO)4 fragments and is isoelectronic with the anionic tetracobalt-indium complex, 27, and the neutral tetracobalt-germanium, - tin, and -lead complexes, 68, 71, and 72. Oxidation of 110 affords 108 (777), while acidification (772) yields the hydride-containing cluster [BiFe3(CO)9(/i-H)3], 111, which also contains a tetrahedral BiFe3 core. Johnson and Lewis (114) have... 

Another catalyst type is the heterogeneous catalyst, which remains as a solid and promotes chemistry at the surface. To function well, they require high surface areas per unit mass. Metal oxides and hydroxides are common examples. A vanadium(V) oxide is employed in the formation of ammonia from nitrogen and hydrogen under elevated temperature and pressure, for example. Polyoxometallate metal clusters, which are oxo-ligand coordination complexes employing dominantly 02 and HO as ligands, have some catalytic roles. 

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