Triammines

Bismuth trichloride shows considerable tendency to form addition compounds. Reaction with ammonia yields the colodess, easily volatili2ed bismuth trichloride triammine [66172-89-2] BiCl ANH, as well as the red, thermally unstable bismuth trichloride hemiammine [66172-90-5] 2BiCl2 NH. Compounds of formula BiCl NO, BiCl 2N02, and BiCl NOCl may be isolated these are stable in dry air but are decomposed by moisture. Bismuth... 

Bismuth ttiiodide may be prepared by beating stoichiometric quantities of the elements in a sealed tube. It undergoes considerable decomposition at 500°C and is almost completely decomposed at 700°C. However, it may be sublimed without decomposition at 3.3 kPa (25 mm Hg). Bismuth ttiiodide is essentially insoluble in cold water and is decomposed by hot water. It is soluble in Hquid ammonia forming a red triammine complex, absolute alcohol (3.5 g/100 g), benzene, toluene, and xylene. It dissolves in hydroiodic acid solutions from which hydrogen tetraiodobismuthate(Ill) [66214-37-7] HBil 4H2O, may be crystallized, and it dissolves in potassium iodide solutions to yield the red compound, potassium tetraiodobismuthate(Ill) [39775-75-2] KBil. Compounds of the type tripotassium bismuth hexaiodide [66214-36-6] K Bil, are also known. 

Cobalt, tetraamminepyrophosphato-structures, 1, 202, 203 Cobalt, tetraammine(sarcosine)-chirality, 1,198 Cobalt, triammine-structure, 1, 8—10 Cobalt, tricarbonato-reactions, 1,22 Cobalt, tricarbonylnitroso-exchange reactions, 1, 290 Cobalt, trichloro-equilibrium constant, 1, 517 Cobalt, trichlorobis(triethylphosphine)-structure, 1, 45... 

Sodium triammine, 4581 Sulfinyl bromide, 0274 Sulfinyl chloride, Dimethylformamide, 4096 Sulfinyl chloride, Tetrahydrofuran, 4096 f Sulfur, Limonene, 4897 Terephthaloyl chloride, 2889... 

When added to a dilute solution of caustic soda or caustic potash, it forms [Sb(OH)6] ion in the solution, from which the sodium or potassium salt, NaSb(OH)e or KSb(OH)6 crystaUizes out. It forms two adducts with ammonia, a red triammine, SbCls 3NHs, and a colorless tetraammine, SbCls 4NHs. SbCls dissociates on heating to trichloride and chlorine dissociation comenc-ing around 120°C and completing at 300°C. 

Biltz 4 carried out a series of investigations on the vapour pressures of solutions of silver chloride and ammonia, and came to the conclusion that silver chloride forms the triammine, [Ag(NH3)3]Cl, at atmospheric pressure below 20° ., and the sesquiammine, 2AgCl(NH3)3, at temperatures between 20° and 60° C. Above 00° C. silver chloride does not unite with ammonia. 

Ammino-silver Bromides.—Silver bromide, like the chloride, unites with ammonia the triammine, [Ag(NH3)3]Br, the sesquiammine, [Ag2(NH3)a]Br2 or 2AgBr.8NII3, the diammine, [Ag(NH3)2]Br, and the monammine, [Ag(NH3)]Br, have all been obtained. 

Triammino-silver Bromide, [Ag(NH3)3]Br. —Silver bromide treated with liquid ammonia below 4° C. yields the triammine, or it may be formed in solution if the bromide be treated with water saturated with ammonia gas under pressure.7... 

The triammine is a white substance, and on raising the temperature above 4° C. passes into the sesquiamminc, 2AgBr.8NITs. 

Sesquiammino-silver Bromide, 2AgBr.8NH3 or [Ag2(NH3)3]Br2, is obtained from the triammine on heating between 4° and 84° C., or by the action of gaseous ammonia on dry silver bromide. 

Triammino-silver Nitrate, [Ag(NH3)3]N03.—The compound is formed when silver nitrate is exposed to dry ammonia gas much heat is developed, increase in bulk takes place, and sufficient heat may he produced to fuse the mass.3 It exhibits considerable heat of formation, is soluble in water, and loses ammonia on heating, dissociating at 63° C. under ordinary pressure, and is soluble in liquid ammonia below —10° C.4 Only the diammine exists in solution, the triammine being completely dissociated into the diammine and ammonia. 

Silver chlorate forms the triammine, [Ag(NH3)3]C103 silver carbonate the tetramminc, [Ag(NH3)2]2CO 3 and silver oxide itself forms diammino-silver oxide, Ag20.2NH3> and the hydroxide, [Ag(NIi3)2]OII.5 Diammino-silver hydroxide appears to be more strongly dissociated than barium hydroxide.6... 

Lithium bromide also combines with gaseous ammonia to form four solid deliquescent substances. The monammine, [Li(NH3)]Br, is formed above 95° C. the diammine, [Li(NIi3)2]Br, between 87° and 95° C. the triammine, [Li(NH3)3]Br, between 71° and 87° C. and the tetrammine about —18° C.2 Ephraim prepared other ammino-salts of lithium, as, for example, tetrammino-lithium nitrate, [Li(NH3)J(N03), which is a colourless syrup at ordinary temperature and is more stable than the chloride tetrammino-lithium chlorate, [Li(NII3)Ll]C103, which is a fairly mobile liquid and tetrammino-lithium perchlorate, [Li(NH3)4]C104, a white solid which liquefies and decomposes at ordinary temperature.3... 

Thallous halides do not absorb ammonia at ordinary temperature, but in liquid ammonia these salts form triannnino-thallous halides of composition [T1(NH3)3]C1, [Tl(NH3)3]Br.1 The triammino-deriva-tives formed are somewhat soluble in liquid ammonia, and the solubility increases with rise of temperature and increase in atomic weight of the halogens. No lower ammino-derivatives are known. Tliallic halides absorb ammonia gas readily. If ammonia gas is passed into an alcoholic solution of thallic chloride, or if dry ammonia gas is passed over dry thallic chloride, the gas is absorbed and a white crystalline substance is formed of composition [T1(NH3)3]C13. The crystals may be washed with alcohol containing ammonia and then with absolute alcohol, and finally dried in vacuo. On coming in contact with water the triammine is decomposed with precipitation of violet-black oxide thus ... 

The triammine is soluble in hydrochloric acid, forming ammonium thallic chloride, 3NH4C1.T1C13, and on heating decomposes writh loss of ammonia and formation of ammonium chloride and thallous chloride. 

Triammino-antimony Trichloride, [Sb(NH3)3]Cl3, is produced when dry ammonia is passed through a solution of antimony trichloride in acetone.2 A mixture of compounds is apparently formed of which the triammine is the chief. It is a white powdery substance which is stable in air but loses ammonia on heating. 

These salts are purple in colour, and yield a purple solution when dissolved in water. They may be prepared from hydroxo-diaquo-triammino-chromie iodide, [Cr(NH3)3(H20)2(H0)]I2.H20,2 or from chromium tetroxo-triammine, Cr04.8NH3.3... 

Triaquo-triammino-cobaltic Chloride, [Co(NH3)3(H20)3]C13, is produced by dissolving trinitrato-triammine cobalt in water with the addition of a little acetic acid and allowing the liquid to stand for twenty hours. It is then cooled and treated with hydrochloric acid at 0° C., when a yellowish-red crystalline powder is precipitated. This is quickly separated from the mother-liquor and dried on a porous plate.2 Other triaquo-triammino-salts have been prepared. 

The trinitro-triammine cobalt has practically no conductivity.3 Werner s theory is further supported by the fact that by the introduction of a fourth molecule of ammonia into the triacido-triammine compound the solution becomes once more conducting, as one (N02) group is displaced from the co-ordination complex. The eobalt-ammino-compounds, therefore, containing fewer than three ammino-radicles, contain non-ionisable acidic radicle, and those containing more than three contain ionisable acidic radicles. The generalisation made in connection with the triammino-eompounds led, therefore, to the establishment of the constitution of other ammino-derivatives, and also to the constitution of some of the ammino-salts of divalent and tetravalent metals. 

Many examples of the triacido-triammine cobalt series are known, and isomerism occurs in the group. 

Trinitro-triammino-cobalt, [Co(NH3)3(N02)3], was the first member of the series prepared. It is best prepared by treating a solution of eobaltous chloride with an ammoniacal solution of sodium nitrite and oxidising the mixture by means of air. The liquid after oxidation is allowed to stand for some days, when crystals separate these are filtered and washed with cold water to free them from chloride, and dissolved in hot water containing a little acetic acid. On cooling the acid liquid trinitro-triammine cobalt separates out, and later, from the same solution, the double salt, [Co(NH3)4(N02)2][Cb(NH3)2(N02)4], separates.1... 

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