Bis ethylenediamine nickel II Chloride

Grossmann and Schiick1 obtained bis(ethylenediamine)-nickel(II) chloride (m.p. 157°) by concentrating and cooling a solution containing nickel(II) chloride and ethylenedi-amine in a 1 2 mol ratio, while Kurnakow2 obtained only sticky, blue residues by a similar procedure. The latter result seems to be the more usual. The procedure described here is based upon a redistribution of ligands in methanol solution and precipitation of the complex by the addition of acetone. 

Five grams of nickel(II) chloride 6-hydrate and 12.1 g. of tris(ethylenediamine)nickel(II) chloride 2-hydrate J are gently refluxed for 5 minutes with a mixture of 47.5 ml. of methanol and 2.5 ml. of water, shaking at first until all the salts are dissolved. A beautiful deep blue solution results. This is filtered by gravity while still warm into a 400-ml. beaker, and the flask and paper are washed once with 5 ml. of hot methanol. Seed crystals are obtained by adding 3 to 4 ml. of acetone slowly to 2 to 3 ml. of the blue solution and scratching or shaking until crystals form the separation of two liquid phases indicates the addition of too much acetone and makes the formation of crystals difficult. 

Fifty milliliters of acetone is added from a dropping funnel in the coruse of 3 or 4 minutes to the bulk of the 

Stirring is continued for 10 minutes after the addition of the last of the acetone. The precipitated product is collected by suction on a coarse, sintered-glass crucible, washed twice with 15 to 20-ml. portions of acetone, and dried by placing in a 100 to 105° oven for hour. The yield is 11 g. (84%). Equally satisfactory results are obtained if all quantities are doubled. Anal. Calcd. for Ni(en)2Cl2 Ni, 23.50 Cl, 28.39. Found Ni, 23.54, 23.53 Cl, 28.45, 28.41. 

Bis(ethylenediamine)nickel(II) chloride consists of pale blue prisms. It is very soluble in water, readily soluble in methanol, and only slightly soluble in acetone and absolute ethanol, but somewhat more soluble in 95% ethanol. In contrast to the 1-hydrate reported by Grossmann and Schuck, the substance does not melt below 300° but appears to undergo a decomposition at about 290°, gradually changing to a white crystalline material. 

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These two compounds are of use as starting materials in the preparation of bis (ethylenediamine) nickel (II) chloride and bis(propylenediamine)nickel(II) chloride 1-hydrate. 

Bis (ethylenediamine)copper (II) diiodocuprate(I), 5 16, 17 Bis (ethylenediam ine) copper (II) iodide, formation of, from bis-(ethy lenediamine) copper (II) diiodocuprate(I), 5 18 Bis(ethylenediamine)nickel(II) chloride, 6 198 Bismuth(III) iodide, 4 114 Bismuth magnesium nitrate, 2Bi-(N0,)3-3Mg(N0,), 24H,0, separation of europium from samarium and gadolinium by, 2 57... 

All solutions were prepared from reagent grade chemicals and solvents without further purification. Two of the new ligands which were tested for the Pfeiffer effect, 2-(2-pyridyl)-benzimidazoline and 2-(2-pyridyl)-imidazoline, were prepared by the method of Walter and Freiser 18). The other ligand which had to be synthesized, (ethanediylidenetetra-thio)tetraacetate (ETTA), was prepared by the method of Longo et al. 12). Tris(ethylenediamine)nickel(II) chloride was prepared by the method of State 17). Bis(salicylidene)triethylenetetramine alumi-num(III) iodide [A1(TS2)]I was prepared by the method of Das Sarma and Bailar 6). 

The tetradentate ligand, 1,4,8,11-tetraazacyclotetradecane (cyclam), forms solid diamagnetic orange to brown Ni(II) complexes with iodide and perchlorate anions (9). When the anions are changed to chloride and bromide, the solid complexes are paramagnetic (9). However, all the complexes are soluble in water, methanol, and benzene, giving yellow solutions. The yellow color remains on treatment with 12N HCl and excess chloride ion (9). It is interesting to note that this amine is a derivative of a reduction product of the template syntheses between bis(ethylenediamine)-nickel(II) and acetone reported earlier. 

Bis(4-imino-2-pentanonato)nickel(II), synthesis 60 Tris(ethylenediamine)platinum(IV) chloride, synthesis 62 cis-Dichloro(ethylenediamine)platinum(Il), synthesis 63 cis- and Tetrachlorobis(diethyl sulfide)platinum(IV), synthesis 64... 

To 1600 mL of methanol in a 3-L flask is added 58 g (0.33 mole) of A, iV -bis-(3-aminopropyl)ethylenediamine and, dropwise, 32.8 g (0.33 mole) of concentrated hydrochloric acid. The solution is cooled to 5° and stirred while 28.7 g (0.33 mole) of 2,3-butanedione is added. After 30 minutes the flask is removed from the ice bath and allowed to stand at room temperature. After a further 20 minutes the solution is pale orange and 82.6 g (0.33 mole) of nickel(II) acetate tetrahydrate is added. The mixture is stirred for 4 hours and 35 mL of concentrated hydrochloric acid is added to the deep red-brown solution. Addition of 45.4 g (0.33 mole) of zinc chloride produces an immediate red-brown precipitate, which is collected by filtration and washed thoroughly wtih diethyl ether. The yield is 110-120 g (68-74%). Anal Calcd. for Ci2H24N4Cl4ZnNi Ci 29.39, H, 4.90 N, 11.43 Cl, 28.95. Found C, 29.25 H, 5.10 N, 11.30 Cl, 28.41. 

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