Lanthanides hydrogenation

There has been one report on the preparation of californium hydrides [235]. The hydrides were prepared by reaction of californium metal with hydrogen at elevated temperatures. It was believed that the stoichiometries were close to that for the dihydride (CfHj+The products exhibited fee structures with an average lattice parameter of Oo = 0.5285 nm, which is slightly larger than expected for the compound based on extrapolations of parameters for preceding actinide dihydrides. This larger parameter and the inability to prepare a trihydride of californium were believed to reflect a tendency for californium to be divalent In the lanthanide-hydrogen system, the hydrides of divalent europium and ytterbium metals deviate from the behavior of the other lanthanide hydrides [149]. 

The lanthanides can form hydrides (qv) of any composition up to LnH. Lanthanide hydrides can desorb hydrogen reversibly with temperature. Therefore, the lanthanides and some of thek alloys ate good candidates for hydrogen (qv) storage, of which LaNi is probably the most promising (see... 

It is easy to reduce anhydrous rare-earth hatides to the metal by reaction of mote electropositive metals such as calcium, lithium, sodium, potassium, and aluminum. Electrolytic reduction is an alternative in the production of the light lanthanide metals, including didymium, a Nd—Pt mixture. The rare-earth metals have a great affinity for oxygen, sulfur, nitrogen, carbon, silicon, boron, phosphoms, and hydrogen at elevated temperature and remove these elements from most other metals. 

The reaetion between Ha and the gently heated (300-350°C) metals produees blaek, reaetive and highly eondueting solids, LnHa. These hydrides have the fee fluorite strueture (p. 118) and are evidently eomposed of Ln , 2H , e , the eleetron being deloealized in a metallie eonduetion band. Further hydrogen ean be aeeommodated in the interstiees of the lattiee and, with the exeep-tions of Eu and Yb, whieh are the two lanthanides... 

The coordination chemistry of the large, electropositive Ln ions is complicated, especially in solution, by ill-defined stereochemistries and uncertain coordination numbers. This is well illustrated by the aquo ions themselves.These are known for all the lanthanides, providing the solutions are moderately acidic to prevent hydrolysis, with hydration numbers probably about 8 or 9 but with reported values depending on the methods used to measure them. It is likely that the primary hydration number decreases as the cationic radius falls across the series. However, confusion arises because the polarization of the H2O molecules attached directly to the cation facilitates hydrogen bonding to other H2O molecules. As this tendency will be the greater, the smaller the cation, it is quite reasonable that the secondary hydration number increases across the series. 

A mercury cathode finds widespread application for separations by constant current electrolysis. The most important use is the separation of the alkali and alkaline-earth metals, Al, Be, Mg, Ta, V, Zr, W, U, and the lanthanides from such elements as Fe, Cr, Ni, Co, Zn, Mo, Cd, Cu, Sn, Bi, Ag, Ge, Pd, Pt, Au, Rh, Ir, and Tl, which can, under suitable conditions, be deposited on a mercury cathode. The method is therefore of particular value for the determination of Al, etc., in steels and alloys it is also applied in the separation of iron from such elements as titanium, vanadium, and uranium. In an uncontrolled constant-current electrolysis in an acid medium the cathode potential is limited by the potential at which hydrogen ion is reduced the overpotential of hydrogen on mercury is high (about 0.8 volt), and consequently more metals are deposited from an acid solution at a mercury cathode than with a platinum cathode.10... 

Molecular hydrogen is rather unreactive at ambient conditions, but many transition and lanthanide metal ions are able to bind and therefore activate H2, which results in transformation into H (hydride) 11 (hydrogen radical) or H+ (proton), and subsequent transfer of these forms of hydrogen to the substrate.7,8 In this context, not only metal hydride but also dihydrogen complexes of transition metal ions, play a key role,9 10 especially since the first structural characterization of one of these species in 1984 by Kubas.11... 

On the other hand, lanthanides with 100% isotopical purity such as terbium or holmium are preferred to simplify the operation and minimize decoherence in spin qubits. In this respect, the existence, for some lanthanides, of a manifold of electronuclear states can provide additional resources for the implementation of multiple qubit states within the same molecule [31]. All atoms in the first coordination sphere should be oxygen, and the sample should be deuter-ated if the compound contains hydrogen, to avoid interaction with other nuclei spins. Again, POM chemistry has been shown to provide ideal examples of this kind. 

Although transition metal-mediated P-H addition across ordinary alkenes proceeds well only with five-membered cyclic hydrogen phosphonates, addition across the olefinic linkage of a,P-unsaturated compounds occurs readily with a range of phosphorus species and catalytic agents. Of particular note are the reaction systems involving platinum,96-107 palladium,108-115 and the lanthanides.116-122... 

In this reaction, a rhodium atom complexed to a chiral diphosphine ligand ( P—P ) catalyzes the hydrogenation of a prochiral enamide, with essentially complete enan-tioselectivity and limiting kinetic rates exceeding hundreds of catalyst turnovers per second. While precious metals such as Ru, Rh, and Ir are notably effective for catalysis of hydrogenation reactions, many other transition-metal and lanthanide complexes exhibit similar potency. 

Airco A modification of the Deacon process for oxidizing hydrogen chloride to chlorine. The copper catalyst is modified with lanthanides and used in a reversing flow reactor without the need for external heat. Developed by the Air Reduction Company from the late 1930s. U.S. Patents 2,204,172 2,312,952 2,271,056 2,447,834. 

Hydrogenation with Early Transition Metal, Lanthanide and Actinide Complexes... 

In hydrogenation, early transition-metal catalysts are mainly based on metallocene complexes, and particularly the Group IV metallocenes. Nonetheless, Group III, lanthanide and even actinide complexes as well as later metals (Groups V-VII) have also been used. The active species can be stabilized by other bulky ligands such as those derived from 2,6-disubstituted phenols (aryl-oxy) or silica (siloxy) (vide infra). Moreover, the catalytic activity of these systems is not limited to the hydrogenation of alkenes, but can be used for the hydrogenation of aromatics, alkynes and imines. These systems have also been developed very successfully into their enantioselective versions. 

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