Ytterbium preparation

The element was first prepared by Klemm and bonner in 1937 by reducing ytterbium trichloride with potassium. Their metal was mixed, however, with KCl. Daane, Dennison, and Spedding prepared a much purer from in 1953 from which the chemical and physical properties of the element could be determined. 

Kobayashi et al. have reported the use of a chiral lanthanide(III) catalyst for the Diels-Alder reaction [51] (Scheme 1.63, Table 1.26). Catalyst 33 was prepared from bi-naphthol, lanthanide triflate, and ds-l,2,6-trimethylpiperidine (Scheme 1.62). When the chiral catalyst prepared from ytterbium triflate (Yb(OTf)3) and the lithium or sodium salt of binaphthol was used, less than 10% ee was obtained, so the amine exerts a great effect on the enantioselectivity. After extensive screening of amines, ds-1,2,6-... 

Nakagawa and coworkers reported a chiral ytterbium catalyst 34 which was prepared from l,l -(2,2 -bisacylamino)binaphthalene and Yb(OTf)3 in the presence of diisopro-pylethylamine by a method similar to that used for Kobayashi s chiral ytterbium reagent [52] (Scheme 1.65, Table 1.66). The amine also plays an important role in this reaction, because racemic cycloadducts were obtained without the tert-amine. Reduc-... 

Among the J ,J -DBFOX/Ph-transition(II) metal complex catalysts examined in nitrone cydoadditions, the anhydrous J ,J -DBFOX/Ph complex catalyst prepared from Ni(C104)2 or Fe(C104)2 provided equally excellent results. For example, in the presence of 10 mol% of the anhydrous nickel(II) complex catalyst R,R-DBFOX/Ph-Ni(C104)2, which was prepared in-situ from J ,J -DBFOX/Ph ligand, NiBr2, and 2 equimolar amounts of AgC104 in dichloromethane, the reaction of 3-crotonoyl-2-oxazolidinone with N-benzylidenemethylamine N-oxide at room temperature produced the 3,4-trans-isoxazolidine (63% yield) in near perfect endo selectivity (endo/exo=99 l) and enantioselectivity in favor for the 3S,4J ,5S enantiomer (>99% ee for the endo isomer. Scheme 7.21). The copper(II) perchlorate complex showed no catalytic activity, however, whereas the ytterbium(III) triflate complex led to the formation of racemic cycloadducts. 

While ytterbium(II) benzamidinate complexes have been known for many years/ the synthesis of the first divalent samarium bis(amidinate) required the use of a sterically hindered amidinate ligand, [HC(NDipp)2l (Dipp = C6H3Pr2-2,6)/ As illustrated in Scheme 54, the dark green compound Sm(DippForm)2(THF)2 (DippForm = [HC(NDipp)2] ) can be prepared by three different synthetic routes. Structural data indicated that hexacoordinated... 

Zeijden [112] used chiral M-functionalized cyclopentadiene ligands to prepare a series of transition metal complexes. The zirconium derivative (82 in Scheme 46), as a moderate Lewis acid, catalyzed the Diels-Alder reaction between methacroleine and cyclopentadiene, with 72% de but no measurable enantiomeric excess. Nakagawa [113] reported l,T-(2,2 -bis-acylamino)binaphthalene (83 in Scheme 46) to be effective in the ytterbium-catalyzed asymmetric Diels-Alder reaction between cyclopentadiene and crotonyl-l,3-oxazolidin-2-one. The adduct was obtained with high yield and enantioselectivity (97% yield, endo/exo = 91/9, > 98% ee for the endo adduct). The addition of diisopropylethylamine was necessary to afford high enantioselectivities, since without this additive, the product was essentially... 

All the rare earth metals except samarium, europium, and ytterbium can be prepared in a pure form by reducing their trifluorides with calcium. Magnesium fluoride is less stable than the rare earth fluorides and so magnesium does not figure as a reductant. Lithium forms a fluoride which is stabler than some of the rare earth fluorides and thus finds some use as a reductant. 

In 2001, the preparation of allylytterbium bromide and the synthesis of homoallylic alcohols using allylytterbium bromide were reported.39 393 Ytterbium metal was found to be activated by a catalytic amount of Mel at 0 °C in THF to produce allylytterbium bromide 66 (Equation (11)). The allylation reaction of a wide range of aromatic aldehydes and ketones proceeded at ambient temperature or less in good to high yields (Table 2). Imines also reacted with allylytterbium bromide to afford homoallyl amines (Table 3). 

In the presence of a catalytic amount of chiral lanthanide triflate 63, the reaction of 3-acyl-l,3-oxazolidin-2-ones with cyclopentadiene produces Diels-Alder adducts in high yields and high ee. The chiral lanthanide triflate 63 can be prepared from ytterbium triflate, (R)-( I )-binaphthol, and a tertiary amine. Both enantiomers of the cycloaddition product can be prepared via this chiral lanthanide (III) complex-catalyzed reaction using the same chiral source [(R)-(+)-binaphthol] and an appropriately selected achiral ligand. This achiral ligand serves as an additive to stabilize the catalyst in the sense of preventing the catalyst from aging. Asymmetric catalytic aza Diels-Alder reactions can also be carried out successfully under these conditions (Scheme 5-21).19... 

For further contributions on the dia-stereoselectivity in electropinacolizations, see Ref. [286-295]. Reduction in DMF at a Fig cathode can lead to improved yield and selectivity upon addition of catalytic amounts of tetraalkylammonium salts to the electrolyte. On the basis of preparative scale electrolyses and cyclic voltammetry for that behavior, a mechanism is proposed that involves an initial reduction of the tetraalkylammonium cation with the participation of the electrode material to form a catalyst that favors le reduction routes [296, 297]. Stoichiometric amounts of ytterbium(II), generated by reduction of Yb(III), support the stereospecific coupling of 1,3-dibenzoylpropane to cis-cyclopentane-l,2-diol. However, Yb(III) remains bounded to the pinacol and cannot be released to act as a catalyst. This leads to a loss of stereoselectivity in the course of the reaction [298]. Also, with the addition of a Ce( IV)-complex the stereochemical course of the reduction can be altered [299]. In a weakly acidic solution, the meso/rac ratio in the EHD (electrohy-drodimerization) of acetophenone could be influenced by ultrasonication [300]. Besides phenyl ketone compounds, examples with other aromatic groups have also been published [294, 295, 301, 302]. 

The analogous homoaryl complex, tetrakis(tetrahydrofuran)Hthium tetrakis-(2,6-dimethylphenyl)lutetiate, has been prepared and its structure determined [130). The ytterbium homologue is isomorphous. The molecular geometry of the anion is shown in Fig. 12 and the molecular parameters are summarized in Table 6. 

Coordinated cyanide in [Fe(phen)(CN)4], prepared by chlorine oxidation of K2 Fe(phen)(CN)4], can act as a bridging ligand, for example in the complexes [ Fe(phen)(CN)4 2M-(H20)2] 4H20, where M = Mn or Zn, whose structure is of double zigzag chains, and of bipy analogues. There is similar bridging to ytterbium, as in (phen)2Fe //-CN— YbCl3(H20)— NC 2Fe(phen)2, obtained from the reaction of ytterbium trichloride with [Fe(phen)2(CN)2]. ... 

Recently, rare-earth metal complexes have attracted considerable attention as initiators for the preparation of PLA via ROP of lactides, and promising results were reported in most cases [94—100]. Group 3 members (e.g. scandium, yttrium) and lanthanides such as lutetium, ytterbium, and samarium have been frequently used to develop catalysts for the ROP of lactide. The principal objectives of applying rare-earth complexes as initiators for the preparation of PLAs were to investigate (1) how the spectator ligands would affect the polymerization dynamics (i.e., reaction kinetics, polymer composition, etc.), and (2) the relative catalytic efficiency of lanthanide(II) and (III) towards ROPs. 

Method 10.1b. Feeding of ytterbium marked feed and faecai coiiection and preparation... 

Method 10.1c. Preparation of ytterbium marked feed for anaiysis... 

Recovery of ytterbium from ores involves several processes that are mostly common to all lanthanide metals. These are discussed individually under each rare earth metal. Recovery involves three major steps (1) processing of ores, (2) separation of ytterbium from rare earth mixtures, and (3) preparation of the metal. 

At the end of the 19th century, Urbain, using the fractional crystallization method, prepared 60g of dysprosium oxide after 10,000 crystallizations then, in 1907, after 15,000 successive nitrate crystallizations from nitric solution, he separated lutetium and ytterbium. 

The reduction to the divalent state involves samarium, europium, and ytterbium. In 1906 C. Matignon and E. Gazes obtained samarium(II) chloride by reducing the trichloride with hydrogen. In 1911, G. Urbain and F. Bourion prepared europium(II) chloride by a comparable reduction involving gydrogen, and in 1929 ytterbium(II) chloride was similarly obtained by W. Klemm and W. Schuth. 

Moseley s work not only shed much fight on the periodic system and the relationships between known elements and the radioactive isotopes, but was also a great stimulus in the search for the few elements remaining undiscovered (11). One of the first chemists to utilize the new method was Professor Georges Urbain of Paris, who took his rare earth preparations to Oxford for examination. Moseley showed him the characteristic fines of erbium, thulium, ytterbium, and lutetium, and confirmed in a few days the conclusions which Professor Urbain had made after twenty years... 

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