Rare earth metal species

The protonation of organo-rare-earth metal species through a-bond metathesis plays a key role in many catalytic applications described below. The high reactivity of rare-earth metals for insertion of unsaturated carbon-carbon multiple bonds [18], in conjunction with smooth o-bond metathesis, allows to perform catalytic small molecule synthesis. This route is atom efficient, economic, and opens access to nitrogen-, phosphorous-, silicon-, boron-, and other heteroatom-containing molecules. The most important catalytic applications of organo-rare-earth metals involving the o-bond metathesis process will be discussed in this review. 

The pH effect in chelation is utilized to Hberate metals from thein chelates that have participated in another stage of a process, so that the metal or chelant or both can be separately recovered. Hydrogen ion at low pH displaces copper, eg, which is recovered from the acid bath by electrolysis while the hydrogen form of the chelant is recycled (43). Precipitation of the displaced metal by anions such as oxalate as the pH is lowered (Fig. 4) is utilized in separations of rare earths. Metals can also be displaced as insoluble salts or hydroxides in high pH domains where the pM that can be maintained by the chelate is less than that allowed by the insoluble species (Fig. 3). 

Yamamoto Y,Nakamura I (2005) Nucleophilic Attack by Palladium Species. 14 211-240 Yasuda H (1999) Organo Rare Earth Metal Catalysis for the Living Polymerizations of Polar and Nonpolar Monomers. 2 255-283 Yasuda N, see King AO (2004) 6 205-246... 

This soft, silver white metal reacts with air and water. The oxide is applied in optical glasses with high refractive indices (special lenses for powerful cameras and telescopes). Used for special effects in optoelectronics and electronics. Lanthanum exhibits catalytic properties. It is a component of flint and battery electrodes. Lanthanum boride (LaB6) is the superior electron-emitter for electron microscopes. Lanthanum is the first of the series of 14 lanthanides, also called the "rare-earth" metals, whose inner N shells are filled with electrons. They do not belong on the "red list" of endangered species they are neither rare nor threatened with depletion. China is particularly rich in lanthanide ores. 

Scheme 12.3 Synthesis of rare-earth metal (Ln) surface complexes, that is, heterogenized Ln single-sites, on silica Do = donor ligands, L = monoanionic ligands and M = Al, Mg, Zr or Si M = Si refers to tethered surface species.

The regio- and stereoselective dimerization of terminal alkynes into disubstituted enynes is efficiently catalyzed by rare-earth metal alkyl and hydride complexes, as reported independently by Bercaw et al. and Teuben et al. in 1987 [211,212]. Takaki and coworkers have shown that complexes Ln[N(SiMe3)2]3 when combined with an amine additive (typically, ArNH2 compounds) afford an active species for the... 

As demonstrated in this review, photoinduced electron transfer reactions are accelerated by appropriate third components acting as catalysts when the products of electron transfer form complexes with the catalysts. Such catalysis on electron transfer processes is particularly important to control the redox reactions in which the photoinduced electron transfer processes are involved as the rate-determining steps followed by facile follow-up steps involving cleavage and formation of chemical bonds. Once the thermodynamic properties of the complexation of adds and metal ions are obtained, we can predict the kinetic formulation on the catalytic activity. We have recently found that various metal ions, in particular rare-earth metal ions, act as very effident catalysts in electron transfer reactions of carbonyl compounds [216]. When one thinks about only two-electron reduction of a substrate (A), the reduction and protonation give 9 spedes at different oxidation and protonation states, as shown in Scheme 29. Each species can... 

Active catalyst species or catalysis intermediates can often be trapped by stoichiometric reactions of the precatalyst with the substrate. The following example describes the successful isolation of such an intermediate with participation of Ln-O cr-bonds. Reduction processes mediated by low oxidation states of the lanthanide elements are of special interest in organic synthesis [256]. One of the most intensively studied reactions is the stoichiometric reduction of arylketones by rare earth metals ytterbium and samarium [277]. Thus formed dianions possess high nucleophilic character and excess lanthanide metal can even accomplish complete cleavage of the C-O double bond (Scheme 36). 

Diene polymerization via lanthanide propanolate-based catalytic systems was first reported by U. Pedretti et al. [162], Several types of binary and ternary initiator systems have been developed since the late 1970s (see Table 7), including zz- and zsopropanolalc ligands [162], homo- and heteroleptic lanthanide species [163-165], and different types of organoaluminum cocatalysts [162,166-168]. Despite such extensive studies, structural evidence of the formation of alkylated rare-earth metal centers remained scarce. 

Alkylated rare-earth metal complexes with rare-earth metal centers surrounded exclusively by oxygen donor ligands were reported from facile ligand redistribution processes in 2,6-dimethylphenolate/trialkylaluminum mixtures. As shown in Scheme 29 for the yttrium derivatives Y(0ArMe,II)2[(//-OArMe>H)2AlR2](THF)2 (R= Me, Et), heterobimetallic 1 1-species were ac-... 

X-ray structure analysis revealed a 7-coordinate rare-earth metal center with two asymmetrically / -coordinating tetramethylaluminate ligands, an asymmetrically / -coordinating siloxide ligand and one methyl group of a trimethylaluminum donor molecule (Fig. 28). Such heteroleptic complexes can be regarded as molecular models of covalently bonded alkylated silica surface species. Moreover, isoprene was polymerized in the presence of 1-3 equivalents of diethylaluminum chloride, with highest activities observed for (Cl) (Ln) ratios of 2 1 (Table 12) (Fischbach et al., 2006, personal communication) [150]. 

A rare example of isospecific 3,4-polymerization of isoprene mediated by a constrained-geometry rare-earth metal initiator was reported by Z. Hou [270]. Binuclear silyl-linked cyclopentadienyl phosphido lanthanide dialkyl complexes were synthesized in good yields and activated with an equimolar amount of [Ph3C] [B(C6Fs)4] (Scheme 68). Cationic alkyl species were proposed as intermediates and an activation scenario was presented based on DFT calculations [270]. 

Solution grafting has been the predominant approach for the immobilization of rare-earth metal precatalyst components [288]. The identification of the catalytically active surface species, commonly formed upon interaction with organoaluminum compounds, is difficult and assisted by molecular model complexes. Several types of support materials including magnesium chloride [289], silica [290], and organic (co-)polymers [291,292], were examined both in the gas-phase and the slurry polymerization of 1,3-dienes. 

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