Lanthanide mixed salts preparation

Inspection of the proposed nitration mechanism (Scheme 1) reveals that the mononitrate dipositive lanthanide species [Ln(H20)x(N03)](0Tf)2 (1) is the key intermediate. An independent preparation and characterisation of such a species enables possible indentification of 1 directly in situ in the reaction mixture. Additionally, spectroscopic examination of these salts may provide some evidence for our working model. We have developed a novel preparation of these mixed salts by simple metathesis of lanthanide chlorides with the requisite quantities of silver nitrate and silver triflate in water (Scheme 3).17 The resulting hydrated salts were white or lightly coloured (pink, green or yellow) solids which were found to be stable indefinitely at room temperature in the solid state. 

Comparable recent detailed reviews of the actinide halides could not be found. The structures of actinide fluorides, both binary fluorides and combinations of these with main-group elements with emphasis on lattice parameters and coordination poly-hedra, were reviewed by Penneman et al. (1973). The chemical thermodynamics of actinide binary halides, oxide halides, and alkali-metal mixed salts were reviewed by Fuger et al. (1983), and while the preparation of high-purity actinide metals and compounds was discussed by Muller and Spirlet (1985), actinide-halide compounds were hardly mentioned. Raman and absorption spectroscopy of actinide tri- and tetrahalides are discussed in a review by Wilmarth and Peterson (1991). Actinide halides, reviewed by element, are considered in detail in the two volume treatise by Katzet al. (1986). The thermochemical and oxidation-reduction properties of lanthanides and actinides are discussed elsewhere in this volume [in the chapter by Morss (ch. 122)]. 

No, the editor didn t know what this name meant either.) It means salts of the triva-lent anions of Group V, restricted in [1] to arsenides, antimonides and bismuthides and prepared by reaction of sodium pnictides with anhydrous halides of transition and lanthanide metals. This violently exothermic reaction may initiate as low as 25°C. Avoidance of hydrated halides is cautioned since these are likely to react uncontrollably on mixing. Another paper includes a similar reaction of phosphides, initiated by grinding [2], Nitrides are reported made from the thermally initiated reaction of sodium azide with metal halides, a very large sealed ampoule is counselled to contain the nitrogen [3],... 

The study of coordination compounds of the lanthanides dates in any practical sense from around 1950, the period when ion-exchange methods were successfully applied to the problem of the separation of the individual lanthanides,131-133 a problem which had existed since 1794 when J. Gadolin prepared mixed rare earths from gadolinite, a lanthanide iron beryllium silicate. Until 1950, separation of the pure lanthanides had depended on tedious and inefficient multiple crystallizations or precipitations, which effectively prevented research on the chemical properties of the individual elements through lack of availability. However, well before 1950, many principal features of lanthanide chemistry were clearly recognized, such as the predominant trivalent state with some examples of divalency and tetravalency, ready formation of hydrated ions and their oxy salts, formation of complex halides,134 and the line-like nature of lanthanide spectra.135... 

Lanthanide complexes of poorly coordinating ligands such as aldehydes and ketones [24], esters [25], and ligands containing sulphur and phosphorus [26] have been prepared. The procedure consists of mixing a solution of hydrated lanthanide salt with a solution of the... 

Phthalocyanines are tetraaza tetrabenzo analogues of porphyrins. Lanthanide complexes with phthalocyanines are prepared by the condensation of phthalonitrile (4 moles) with a lanthanide salt. The monocomplexes were prepared by heating a 1 4 mixture of lanthanide saltiphthalonitrile at 275°C. The molten solution solidified after an hour and purification of the complex is done by removal of excess phthalonitrile and impurities with organic solvents. Final purification is done by chromatography [85]. The bis complexes are prepared in a similar fashion but with a large excess of phthalonitrile [86]. Mixed ligand... 

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