46,0202 H236h HANDBOOK OF PREPARATIVE INORGANIC CHEMISTRY VOLUME 2 + SECOND EDITION Edited hy GEORG BRAUER PROFESSOR OF INORGANIC CHEMISTRY UNIVERSITY OF FREIBURG. TRANSLATED BY SCRIPTA TECHNICA, INC. TRANSLATION EDITOR PAUL G. STECHER MERCK SHARP & DOHME RESEARCH LABORATORIES 1965 @ ACADEMIC PRESS + New York - Londono. GLEMSER 1536 of(NH)4CO.in 500 ml. of H.0 and gs, 00 bubbled through for 2-5 hours, aa . tion, containing sever,; “fter idation, the blood-red solut Tal complete oxidstion js evaporated on a steam bath unti) the yal pieces of (na) 2° "The solution is then filtered, concentrateg 300 ml, and chilled, whereupon ICo(NHa)400 12804 » 3H20 cryeiq” 200 as ned prisms. The mother liquor is decanted; the Precip tue is. filtered off and washed once with a saturated sony! ee ted from a small portion of the precipitate. More salt i prteined by further evaporation of the mother liquor [agg ol (NH,)2CO,). Yield: 92 g. i of into a solution of f of conc, ammonia, and ail Some PROPERTIES: ‘ -red prisms. d 1.892, Formula weight 524.27, Gamet-re te aqueous solution decomposes on standing in light, Forms [Co(N,).” (#20) )804 (tetraammineroseocobalt sulfate) with dil. H.so" Loses all water over conc. HaSOs. Crystal form: orthorhomig” bipyramidal. REFERENCE: 8. M, Jérgensen, Z. anorg. Chem. 2, 281 (1892), Dichlorotetraamminecobalt (lll) Chloride [Co(NHs).Ch]CI Two stable isomeric forms exist: these are the 1,2-dichloro- (cis-) and 1,6-dichloro- (trans-) compounds. 1,2.DICHLOROTETRAAMMINECOBALT (III) CHLORIDE (CIS), [Co(NH3)4ClgIC1 - 0.5420 Treatment of an ammoniacal solution of Co(CHsC0O)2 + 41.0 With NaNO», followed by air oxidation, affords [Co(NHg)«(NO;)aI- NOz, which is converted to the dichloro compound with conc. KCl. Air is bubbled for five hours through a solution of 20. of NaNOg and 20 g. of Co(CH3COO)z + 41,0 in 200 ml. of 20% NHs- The violet solution is concentrated to a small volume with occ sional addition of solid NaHOO,, then chilled, A lange exooss of argohol is added to cause precipitation. ‘The precipitate is filtered off, washed with alcohol-ether, and dried in's vacuum desiccator: silnitrotetraamminecobalt (II) nitrite, which 1s 10!28. COBALT, NICKEL 1537 syNONYM: Formerly: Chlorovioleccobalt chloride PROPERTIES: Formula weight 242.45, Violet water of hydration at 60°C. Very cee Water soluble; loses REFERENCE: c. Duval. Comptes Rendus Hebd. Séances Acad. Sci, 182, 636 (1926). DIAQUOTETRAAMMINECOBALT (I) SULEAT {o(NHs)a(H20)ala(S0q)3 « 3110 = This is formed by treatment with dl, Ha80 4 Of [CONHs) 4C0]-{S0,). + 950 ‘A solution of 5 g. of pure : 100 ml. of cold H20 and 10 mi, TP Ata sC0s] S04 - 90 in results in evolution of CO., 418 prepared; this The clear solution is treated with 50-60 ml. of alcohol, added in small portions, The precipitate is filtered off, washed with 50% alcohol until f 2 inain, Yield: 6.2 g. (theoretical: Oo? gate of acid, and dried PROPERTIES: Formula weight 668.45. Red quadratic prisms, which lose water of crystallization over conc, HzS0, Solubility at 22°C: 0,175 moles/liter of water. REFERENCE: S, M. Jérgensen, Z. anorg. Chem. 2, 296 (1892). 1,6-DICHLOROTETRAAMMINECOBALT (Ill) CHLORIDE (TRANS), (Co(NH3)4ClgICl « H20 A solution of 10 g. of [Co(NH,) 4H20)a]{SO.)5 * 3H20 in 50 ml. of cold conc, H2SO4 is prepared; the flask is allowed to stand for 24 hours, then placed in ice, and 50 ml. of conc. HCl is added dropwise with frequent and vigorous shaking. The trans salt separates in 48 hours. The flask is tilted and the mother liquor decanted as thoroughly as possible. Dilute HCI is then added; the precipitate is filtered off and washed with dil. HCl until free of H2SO4, then washed with alcohol until free of acid. Yield: 7.25 g. (theoretical; 7.53 g.). ‘SYNONYM: Formerly: Chloropraseocobalt chloride.0. GLEMSER 1538 PROPERTIES: : s green crystals, 425 weight 251.46. Lustrou: ls 60, Former of exystallization in 1-2 hours at 1O0rC Solubiiy Loses water of ervs/liter 120; hydration in solution vieaig {Co(NH) 4H,0)2]Cls. The trans compound is more stable jf the cis form. REFERENCE: S. M. Jorgensen, Z. anorg. Chem. 14, 404 (1897). Triethylenediaminecobalt (lll) Bromide [Co en,]Brs ‘The preparation from cobalt salt, ethylenediamine and Nagy yields the racemate of the optically active forms of {Co en,)Br, as the first product. The racemate can be resolved with tartarig acid into the d- and I-tartrate, and further converted to the d- and I-bromide. A) RACEMIC TRIETHYLENEDIAMINECOBALT (111) BROMIDE, (Co eng]Br3 « 320 A solution of 10 g. of CoCl, - 6 HzO in 150 g. of 10% aqueous ethylenediamine is prepared and oxidized by bubbling air through it for several hours. The brown solution is then acidified with HCl and concentrated until crystallization. The crystal mass is dissolved in H,O and treated with NH«NO., which precipitates 1,6-[Co enCl,|NO3. This precipitate is removed by filtration; then NaBr is added to the filtrate, whereupon completely pure (Co ens]Brs - 3H20 separates out. PROPERTIES: Formula weight 533.04, Small yellow needles. M.p. 271% a 1.845. Solubility in HzO at 16°C: 4.33 g. of anhydrous salt per 100 g, of solution, = se B) RESOLUTION WITH TARTARIC ACID A solution of 100 g. the amount of silver tal two atoms of bromine. filtered off and then was! no longer yellow. The of [Co eng]Br3 in water is treated with trate (68.3 g.) needed for reaction with After boiling, the AgBr precipitate is shed with boiling water until the water is filtrate and washings are combined and