Anhydrous Rare Earth Chlorides

Abstract

The preparation of the anhydrous chlorides of the rare earth elements is of considerable interest, since these compounds serve as the starting materials in the preparation of the metals, either directly by electrolysis in the fused state or indirectly by electrolysis in alcoholic solutions with a mercury cathode followed by the subsequent thermal decomposition of the resulting amalgams. The most important methods for the preparation of anhydrous rare earth chlorides previously suggested are : from the metals, by action of dry chlorine, hydrogen chloride, or methyl chloride1 at elevated temperatures; frdm the oxides, by action of chlorine in the presence of a reducing agent,2 by action of hydrogen chloride alone3 or with ~a r b o n ,~ by action of carbon tetra~hloride,~ carbonyl chloride,6 sulfur monochloride vapor7 (or a mixture of sulfur monochloride and chlorine) ,8 by heating with phosphorus penta~hloride,~ by mixing with a slight excess of ammonium chloride and gradually dropping the mixture into a red-hot c r~c i b l e ;~ from the sulfides, by heating in dry hydrogen chloride;1° from the carbides, by heating with chlorine1' or in a current of hydrogen chloride ; I z from the hydrated chlorides, by heating in a current of hydrogen chloride gas,13 by adding ammonium chloride to a solution of the chlorides, evaporating to dryness, and heating in air14 or in a current of HC1, l5 by dehydration in an atmosphere of carbonyl chloride (or a mixture of carbon monoxide and chlorine16), by heating in air and treating the resulting mixture of chlorides and oxychlorides with sulfur monochloride and chlorine or sulfur monochloride, chlorine, and hydrogen chloride mixtures, by extracting the chloride-oxychloride

Enhancing Magnetic Hysteresis in Single-Molecule Magnets by Ligand Functionalization

“…Anhydrous LnCl 3 salts were prepared according to literature procedures. 40 NaH, NaBPh 4 , and (S)-(-)-1-phenylethanol are commercially available and were used without further treatment. Elemental analyses were performed on a Flash 2000 elemental analyzer.…”

Breaking the axiality of pentagonal–bipyramidal dysprosium(iii) single-molecule magnets with pyrazolate ligands

“…Anhydrous DyCl 3 salts were prepared according to literature procedures. 48 NaH, NaBPh 4 , 3-(trifluoromethyl)pyrazole, 3-methylpyrazole, 3-isopropyl-1H-pyrazole, pyrazole, 3,5dimethylpyrazole, and 3,5-diisopropylpyrazole were purchased commercially and used as received without further purification. THF, pyridine, thiazole and hexane were dehydrated and deoxygenated using a solvent purification system prior to use.…”

“…Yield: 287 mg (62% based on Dy). Elemental analysis found (calcd)% for C48 H 65 BClDyN 2 O 5 : C, 59.98 (60.20); H, 6.57 (6.58); N, 2.89 (2.93). Preparation of 3.…”

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

“…The resulting mixture is then transferred into the bulb ( A ) of the apparatus shown in Figure 7 . 347 A is connected to a bent delivery tube ( Figure 7 , C ) equipped with a collection bulb at the end ( Figure 7 , E ); the apparatus is connected to a high-vacuum line via a trap ( Figure 7 , F ) positioned at the end of the apparatus. Once the reactor has been charged with the RECl 3 /NH 4 Cl mixture, the furnace is heated to 300 °C for up to 30 h, affording anhydrous RECl 3 upon sublimation of NH 4 Cl.…”

“… Apparatus for the “dry method” synthesis of anhydrous trivalent RE chlorides. 347 A , pyrex flask; B , furnace; C , delivery tube (internal diameter 28 mm); D , ground glass connection; E , ammonium chloride receiving bulb (500 mL); F , trap (connected via rubber stopper); G–G′ , galvanized-iron cans; H , asbestos; I , asbestos boards; J , asbestos inner cover; K , heating unit (six Westinghouse No. 299-425 space heaters, 110 V and 220 W capacity); L , thermometer; M , pyrex thermometer cover; N , high-vacuum pump connection.…”