Cerium metal transition

The diastereoselectivity of the reaction may be rationalized by assuming a chelation model, which has been developed in the addition of Grignard reagents to enantiomerically pure a-keto acetals7,8. Cerium metal is fixed by chelation between the N-atom, the methoxy O-atom and one of the acetal O-atoms leading to a rigid structure in the transition state of the reaction (see below). Hence, nucleophilic attack from the Si-face of the C-N double bond is favored4. 

The Mott-like transition, a central concept for the description of the actinide metal series, causes the sudden increase of the atomic volumes, encountered when between Pu and Am (Fig. 3). All other properties indicate the onset of a 5f localized behaviour at Am (see Part V) the 5 f pressure, which had contained to smaller values the equilibrium interactinide distance, suddenly gives in, with the withdrawal of the 5f s within the atomic core. The occurrence of such a transition within a series characterized by an unsaturated shell, is a unique phenomenon of the actinide series. In lanthanides, it does not occur except perhaps under pressure in cerium metal the approaching of cerium atoms induces suddenly the itineracy of 4f orbitals and a sudden volume collapse - see Chap. C. Neither it occurs in d-transition metal series, where the atomic volumes have an almost parabolic behaviour when plotted vs. Z (see Fig. 3 and Chap. C). The current... 

Cerium metal is discussed in ch. 4 and only a brief mention of its high pressure behavior will be made here (for references see the list in ch. 4). Cerium can exist at atmospheric pressure in the fee (y) or dhep (iS) form and undergoes an isostructural transition near 100 K to another fcc-form referred to as o-Ce. The y-a Ce transition occurs at 7 kbar at room temperature and this transition is accompanied by about 8% volume decrease. This is one of the most widely studied transitions as a function of pressure and temperature and is believed to involve a valence change from 3 towards a higher valence state (3.7 ). The y to a transition line terminates at a critical point the very first example in which a solid - solid transition was shown to exhibit a liquid-vapor-like critical point. A pressure-induced phase transition near 50 kbar, initially reported to be yet another isostructural transition has been shown to be from fee (a-Ce) to an orthorhombic phase with the a-U structure. Stager and Drickamer (1964) have reported a pronounced resistance anomaly near 120 kbar indicative of a phase transition, but the nature of this transition is unknown. The fusion behavior of Ce is again unique in that it exhibits a minimum. 

Group 3 (IIIB) and Inner Transition-Metal Perchlorates. The rare-earth metal perchlorates of yttrium and lanthanum have been reported (53). Tetravalent cerium perchlorate [14338-93-3] 06(0.04)4, and uranium perchlorate have also been identified (54). 

The transition-metal and rare-earth core-line XPS spectra show little, if any, BE shifts at all. Nevertheless, information about atomic charge and valence states can be extracted by examining other features in the spectra. The plasmon loss satellite intensity found in the spectra of Co-containing compounds provides a particularly useful handle on the Co charge. The lineshapes of RE spectra are characteristic of their valence state, as seen in the distinction between trivalent and tetravalent cerium in CeFe4Pni2 compounds. 

Catalyst systems for the WGS reaction that have recently received significant attention are the cerium oxides, mostly loaded with noble metals, especially platinum 42—46]. Jacobs et al. [44] even claim that it is probable that promoted ceria catalysts with the right development should realize higher CO conversions than the commercial Cu0-Zn0-Al203 catalysts. Ceria doped with transition metals such as Ni, Cu, Fe, and Co are also very interesting catalysts 37,43—471, especially the copper-ceria catalysts that have been found to perform excellently in the WGS reaction, as reported by Li et al. [37], They have found that the copper-ceria catalysts are more stable than other Cu-based LT WGS catalysts and at least as active as the precious metal-ceria catalysts. 

Cerium(IV) oxidations of organic substrates are often catalysed by transition metal ions. The oxidation of formaldehyde to formic acid by cerium(IV) has been shown to be catalysed by iridium(III). The observed kinetics can be explained in terms of an outer-sphere association of the oxidant, substrate, and catalyst in a pre-equilibrium, followed by electron transfer, to generate Ce "(S)Ir", where S is the hydrated form of formaldehyde H2C(OH)2- This is followed by electron transfer from S to Ir(IV) and loss of H+ to generate the H2C(0H)0 radical, which is then oxidized by Ce(IV) in a fast step to the products. Ir(III) catalyses the A -bromobenzamide oxidation of mandelic acid and A -bromosuccinimide oxidation of cycloheptanol in acidic solutions. ... 

Symbol Nd atomic number 60 atomic weight 144.24 a rare earth lanthanide element a hght rare earth metal of cerium group an inner transition metal characterized by partially filled 4/ subshell electron configuration [Xe]4/35di6s2 most common valence state -i-3 other oxidation state +2 standard electrode potential, Nd + -i- 3e -2.323 V atomic radius 1.821 A (for CN 12) ionic radius, Nd + 0.995A atomic volume 20.60 cc/mol ionization potential 6.31 eV seven stable isotopes Nd-142 (27.13%), Nd-143 (12.20%), Nd-144 (23.87%), Nd-145 (8.29%), Nd-146 (17.18%), Nd-148 (5.72%), Nd-150 (5.60%) twenty-three radioisotopes are known in the mass range 127-141, 147, 149, 151-156. 

When the itinerant state is formed, a volume collapse AV/V is always encountered, as predicted by the theory of the preceding sections. In one of the lanthanides, cerium, this volume collapse is particularly accentuated for its isostructural transition from the y to the a form, possibly associated with a change in metallic valence from three to four (both oxidation numbers are stable in cerium chemistry) (see Fig. 1 of Chap. A),... 

The three basic ground state properties of the heavy actinides are more likely to follow those of the rare earths (Fig. 2 of Chap. A). The atomic volumes of the rare earth metals decrease monotonically with atomic number. This suggests, as will be explained more fully below, that the 4f electrons make little or no contribution to cohesion. They are said to be on the low density side of a Mott transition - with the notable exception of one of the phases of cerium. This is believed to be also the case for the second half of the actinide series ... 

In a somewhat different approach, Asahi Glass KK have claimed [132] that the addition of a transition metal salt (e. g., cobalt-, copper-, lead-, cerium-, bismuth-, manganese-, chromium-, iron- chloride, or cobalt fluoride, etc.) greatly improves the ECF production of perfluorobicyclic compounds, derived from naphthalene, indene, benzofuran, phthalimide, indole, quinolizine, benzotriazole, and quinoline. 

Therefore, based on available literature, the following sorption results were expected (l) as a result of the smectite minerals, the sorption capacity of the red clay would be primarily due to ion exchange associated with the smectites and would be on the order of 0.8 to I.5 mi Hi equivalents per gram (2) also as a result of the smectite minerals, the distribution coefficients for nuclides such as cesium, strontium, barium, and cerium would be between 10 and 100 ml/gm for solution-phase concentrations on the order of 10"3 mg-atom/ml (3) as a result of the hydrous oxides, the distribution coefficients for nuclides such as strontium, barium, and some transition metals would be on the order of 10 ml/gm or greater for solution-phase concentrations on the order of 10 7 mg-atom/ml and less (U) also as a result of the hydrous oxides, the solution-phase pH would strongly influence the distribution coefficients for most nuclides except the alkali metals (5) as a result of both smectites and hydrous oxides being present, the sorption equilibrium data would probably reflect the influence of multiple sorption mechanisms. As discussed below, the experimental results were indeed similar to those which were expected. 

The typical display of the inner transition metals. The count of elements in the sixth period goes from lanthanum (La, 57) to cerium (Ce, 58) on through to lutetium (Lu, 71) and then back to hafnium (Hf, 72). A similar jump is made in the seventh period. 

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