Lanthanide elements metallic compounds

Of course, the fascinating steric features of lanthanide elements are most impressively expressed in the lanthanide contraction [76]. In textbooks, lanthanide contraction is often simply explained as being the phenomena responsible for similar chemical properties, in particular between the pairs of the d-transition metal homologues Zr/Hf, Nb/Ta and Mo/W. However, what does the contraction mean to the lanthanide elements (and compounds derived from them)... 

Recent advances in the techniques of photoelectron spectroscopy (7) are making it possible to observe ionization from incompletely filled shells of valence elctrons, such as the 3d shell in compounds of first-transition-series elements (2—4) and the 4/ shell in lanthanides (5, 6). It is certain that the study of such ionisations will give much information of interest to chemists. Unfortunately, however, the interpretation of spectra from open-shell molecules is more difficult than for closed-shell species, since, even in the simple one-electron approach to photoelectron spectra, each orbital shell may give rise to several states on ionisation (7). This phenomenon has been particularly studied in the ionisation of core electrons, where for example a molecule (or complex ion in the solid state) with initial spin Si can generate two distinct states, with spin S2=Si — or Si + on ionisation from a non-degenerate core level (8). The analogous effect in valence-shell ionisation was seen by Wertheim et al. in the 4/ band of lanthanide tri-fluorides, LnF3 (9). More recent spectra of lanthanide elements and compounds (6, 9), show a partial resolution of different orbital states, in addition to spin-multiplicity effects. Different orbital states have also been resolved in gas-phase photoelectron spectra of transition-metal sandwich compounds, such as bis-(rr-cyclo-pentadienyl) complexes (3, 4). 

The actinide element series, like the lanthanide series, is characterized by the filling of an f-electron shell. The chemical and physical properties, however, are quite different between these two series of f-electron elements, especially in the first half of the series. The differences are mainly due to the different radial extension of the 4f- and 5f-electron wavefunctions. For the rare-earth ions, even in metallic systems, the 4f electrons are spatially well localized near the ion sites. Photoemission spectra of the f electrons in lanthanide elements and compounds always show "final state multiplet" structure (3), spectra that result from partially filled shells of localized electrons. In contrast, the 5f electrons are not so well localized. They experience a smaller coulomb correlation interaction than the 4f electrons in the rare earths and stronger hybridization with the 6d- and 7s-derived conduction bands. The 5f s thus... 

Thus the rather easily obtained atomic sizes are the best indicator of what the f-electrons are doing. It has been noted that for all metallic compounds in the literature where an f-band is believed not to occur, that the lanthanide and actinide lattice parameters appear to be identical within experimental error (12). This actually raises the question as to why the lanthanide and actinide contractions (no f-bands) for the pure elements are different. Analogies to the compounds and to the identical sizes of the 4d- and 5d- electron metals would suggest otherwise. The useful point here is that since the 4f- and 5f-compounds have the same lattice parameters when f-bands are not present, it simplifies following the systematics and clearly demonstrates that actinides are worthy of that name. 

Samarium ore usually is digested with concentrated sulfuric or hydrochloric acid. The extraction process is similar to other lanthanide elements. Recovery of the metal generally consists of three basic steps. These are (1) opening the ore, (2) separation of rare earths first to various fractions and finally to their individual compounds, usually oxides or halides, and (3) reduc-... 

Before continuing, some words must be said with regard to the terms rare earths and f elements used in this chapter. The term rare earths includes the elements Sc, Y and the lanthanides La through Lu. However, this chapter solely deals with divalent or trivalent rare-earth ions which are optically active, i.e., possess a partially filled f-shell. Thus, although the term rare earths is used in this chapter, it should be kept in mind that the elements Sc, Y, La, and Lu are excluded. In some exceptional cases the more general term f elements will be used, as for example when high pressure studies on actinide ions with a partially filled 5f shell are discussed. There are only few studies on 5f elements in non-metallic compounds under pressure, however, it seems interesting to compare the results found for these ions with those for the 4f-elements. 

The use of unsubstituted or 4-methyl phenols resulted in the formation of cluster compounds [58]. However, 2,6-di(fcrt-butyl) substituted aryloxide ligands allowed the isolation of mononuclear 3-coordinate homoleptie complexes of the lanthanide elements, the coordination mode of which was first demonstrated with the N(SiMe3)2 ligand [59], The 2,6-substitution pattern is very effective because the alkyl groups are directed towards the metal center and impose a steric coordination number onto the metal which is comparable to the Cp ligand (Cp 2.49 OC6H3rBu2-2,6 2.41) [60],... 

The radius of the 24-coordinate metal site in MB6 is too large (M-B distances are in the range of 215-25 pm) to be comfortably occupied by the later (smaller) lanthanide elements Ho, Er, Tm, and Lu, and these elements form MB4 compounds instead, where the M-B distances vary within the range of 185-200 pm. 

As a group of typical metal elements, lanthanide elements can form chemical bonds with most nonmetal elements. Some low-valence lanthanide elements can form chemical bonds in organometallic or atom cluster compounds. Because lanthanide elements lack sufficient electrons and show a strong repulsive force towards a positive charge, chemical bonds between lanthanide metals have not yet been observed. Table 1.4 shows that 1391 structure-characterized lanthanide complexes were reported in publications between 1935 and 1995 and these are sorted by chemical bond type. 

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