Chloride ammino

The solid readily dissolves chemically in concentrated hydrochloric acid, forming a complex, and in ammonia as the colourless, linear, complex cation [H3N -> Cu <- NHj] (cf AgCl) if air is absent (in the presence of air, this is oxidis to a blue ammino-copper(II) complex). This solution of ammoniacal copper(I) chloride is a good solvent or carbon monoxide, forming an addition compound CuCl. CO. H2O, and as such is used in gas analysis. On passing ethyne through the ammoniacal solution, a red-brown precipitate of hydrated copper(I) dicarbide (explosive when dry) is obtained ... 

The importance of the theory was further demonstrated by the discovery of the existence of optically active inorganic compounds, and the isolation of the exact number of optical isomers theoretically possible for the spatial arrangement of the atoms.1 Friend 2 and others criticised the theory on the grounds that in simple compounds, such as sodium chloride or cobaltous chloride, the chlorine is ionised and yet is attached to sodium or cobalt atom directly, whereas in the ammino-coinpounds the acid capable of ionisation is that which is not directly attached to metal. For instance, in chloro-pentammino-cobaltic chloride, [CoCI(NH3)5]C12, it is the chlorine outside the first zone which is ionised in solution. Also, the dissociable acidic groups are not attached to any point within the complex, but simply hover round the central complex in an indefinite manner. Thus a definite valency for ionisable... 

Complexes are also known in which the co-ordination numbers- are one, two, three, five, seven, and even eight respectively, but these are less frequent. As examples may be mentioned sulphito-coppcr potassium, [Cu(S03)]K, and the unstable nitroso-ferrous sulphate, [Fe(N0)]S04, each of which possess unit co-ordination number. l)i-ammino-silvcr chloride, [Ag(NH3)2]Cl, and triammino-silver chloride. [Ag(NIT3)3]Cl, possess co-ordination numbers two and three respectively. In penta-phenylhydrazino-zine sulphate, [Zn(NHa.NH.C6II5)5JS04, and octammino-strontium chloride, [Sr(NH3)8]Cl2, the co-ordination numbers are five and eight respectively. 

Werner and Kling 1 found that two such isomers can be obtained from the m-salt of type [M(NII3)4R2]R. They prepared the compounds l-chloro-2-ammino-diethylenediamino-cobaltie chloride, 1 Werner and Kling, Ber., 1911, 44, 1887 1912, 45, 3287. 

After the resolution of 1-2-chloro-ammino-diethylenediamino-cobaltie chloride many analogous resolutions of optically active compounds of octahedral symmetry were carried out, and active isomers of substances containing central cobalt, chromium, platinum, rhodium, iron atoms are known. The asymmetry is not confined to ammines alone, but is found in salts of complex type for example, potassium tri-oxalato-chromium, [Cr(Ca04)3]K3, exists in two optically active forms. These forms were separated by Werner2 by means of the base strychnine. More than forty series of compounds possessing octahedral symmetry have been proved to exist in optically active forms, so that the spatial configuration for co-ordination number six is firmly established. 

Ammino-salts of Cupric Halides.—When an aqueous solution of cupric chloride is treated with an aqueous solution of ammonia the hydroxide is precipitated, but if excess of ammonia be added the precipitate dissolves, forming a deep blue solution. The liquid contains the tetraminino-chloride and higher ammino compounds, depending on the concentration of the ammonia in solution and the temperature. 

Diammino-cupric Chloride, [Cu(NII3)2]C12, is obtained by heating the higher ammino-derivatives to 150° C. or less, or by the action of ammonia on a concentrated solution of cupric chloride, when the diammine is gradually precipitated from the liquid.4... 

Ammino-cupric Bromides.—Cupric bromide, like euprie chloride, absorbs ammonia gas, forming complex ammino-compounds. The following ammines of cupric bromide have been described Hexammino-cupric bromide, [Cu(NH3)6]Br2 pentammino-cupric bromide, [Cu(NH3)5]Br2 diammino-cupric bromide, [Cu(NTI3)2]Br2 and decammino-tricupric bromide, [Cu3(NH3)10]Br8. 

Ammino-cuprous Chlorides.—It has long been known that cuprous chloride is soluble in aqueous ammonia, giving a solution which is capable of absorbing carbon monoxide and hence used in gas analysis. Cuprous chloride is also soluble in liquid ammonia.5... 

At least five different ammino-cuprous chlorides have been described. By studying the vapour pressures obtained by saturating cuprous chloride with ammonia and measuring the vapour pressure between 0° and 150° C., Lloyd found that only three ammino-derivatives existed, namely, hexammino-cuprous chloride, [Cu2(NH3)6]C12 triammino-cuprous chloride, [Cu2(NH3)3]Cl2 monammino-cuprous chloride, [Cu2(NH3)]C12. 

Ammino-cuprous Bromides.—Cuprous bromide forms three definite compounds which correspond to the chlorides, namely, hexammino-cuprous bromide, [Cu2(NTI3)3Br2 triammino-cuprous bromide, [Cu2(NH3)3]Br3 and dianimino-cuproue bromide, [Cu2(NH3)2]Bra. 

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. 

The ammino-iodides of silver show great tendency to form mixed crystals for instance, sesquiammino-silver chloride and monammino-silver chloride form mixed crystals at 30° C.1... 

Ammino - aur ous Chlorides.—Aurous chloride unites with ammonia, forming dodecamrnino-aurous chloride, AuC1.12NH3 triammino-... 

Monammino-aurous chloride is a white crystalline powder, sparingly soluble in water, soluble in an aqueous solution of ammonia, and precipitated by the addition of hydrochloric acid. It is unstable in the dry state, and decomposes completely on heating between 150° and 200° C. Aurous bromide and aurous iodide also unite with ammonia. The former yields only one ammino-derivative, the diammine, [Au(NII3)g]Br, and the latter two ammino-derivatives, namely, heAmmino-aurous iodide, [Au(NH3)6]I, and monammino-aurous iodide, [Au(NH3)]I. 

Ammino-derivatives of Auric Salts and Oxides.—Auric chloride, like platinic chloride, combines with hydrochloric acid and alkali chlorides with formation of ehlorauric acid, HAuC14, and alkali chlor-... 

Sodium and potassium chlorides absorb ammonia, but there is no evidence of chemical reaction, and on exposure to air ammonia is completely lost. If, however, sodium chloride is dissolved in liquid ammonia at —10° C. and the solution evaporated at —24° C., small needle-shaped crystals separate which have a composition corresponding to pentammino-sodium chloride, [Na(NH3)5]Cl. Lithium salts, on the other hand, readily absorb ammonia, forming ammino-dcrivatives. 

Ammino-lithium Halides.—Lithium halides absorb gaseous ammonia in the dry state. The chloride forms four compounds depending on the temperature at which absorption takes place. Below 13° C. tetrammino-lithium chloride, [Li(NH3)4]Cl, is produced. Triam-mino-lithium chloride, [Li(NH3)3]Cl, is formed between 20° and 60° C. diammino-lithium chloride, [Li(NH3)2]Cl, between 60° and 85° C. and at 85° C. the monmnmine, [Li(NH3)]Cl, is produced. These are white unstable substances.1... 

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... 

The ammino-iodidcs behave towards water and heat like the chlorides. 

Zinc halides unite with ammonia, readily forming a number of metal-ammines containing one, two, four, five, or six molecules of ammonia for every molecule of zinc salt. The ammino-derivatives of the chlorides are best known, although some of these described appear to be of doubtful individuality. 

Ammino-zinc Iodides.—These are prepared in the same way as those of zinc chloride. Pentammino-zinc iodide, [Zn(NH3)5]X2, and hc.mmmino-zinc iodide, [Zn(NH3)G I2, are easily obtained. 

Ammino-zinc Nitrates are obtained in the same- way as the ammino-zinc chlorides. By saturating a concentrated solution of zinc nitrate with ammonia at low temperature, a colourless crystalline substance separates which is tetrammino-zinc nitrate, [Zn(NH3)4](N03)2. If more ammonia is used and the temperature is kept below 0° C., hex-ammino-zinc nitrate, [Zn(NH3)6](N03)2, is obtained. 

Ammines of Cadmium Halides.—Cadmium chloride unites with ammonia with formation of the following compounds Mon-ammino-cadmium chloride, [Cd(NH3)]Cl2 diammino-cadmium chloride, [Cd(NH3)a]Cl2 triammino-cadmium chloride, [Cd(NH3)3]Cl2 letram-mino-cadmium chloride, [Cd(NH3)4]Cl2 hexammino-cadmium chloride, [Cd(NH3)6]Cl2A... 

Diammino-cadmium Chloride, [Cd(NH3)2]Cl2, has been obtained in several ways. If cadmium chloride be dissolved in hot aqueous ammonia and the liquid cooled, a crystalline substance separates which is a mixture of diammino-salt and cadmium hydroxide if, however, a clear aqueous solution of cadmium chloride be saturated with ammonia gas and allowed to evaporate spontaneously, the diammine is obtained free from hydroxide. The same ammino-salt is formed by adding a saturated solution of cadmium chloride to liquid ammonia and evaporating off the excess of ammonia by allowing the temperature to rise. The diammine is also formed by passing ammonia gas into an alcoholic solution of cadmium chloride.2... 

Several mercurous salts absorb ammonia in the dry state or react with ammonia in aqueous solution. The products formed have been described from time to time as ammino-mercurous compounds. It appears, however, that these supposed mercuro-ammines are nonexistent, and that the substances produced by the action of ammonia are really mercuric derivatives mixed with mercury. For instance, mercurous fluoride in the dry state is blackened by ammonia gas, forming a compound HgF(NH3). This substance gives off ammonia at 100° C. and is black in colour the colour is now regarded as being due to finely divided mercury, and the compound as a derivative of mercuric fluoride and not of mercurous fluoride. Numerous instances of the same kind may be quoted. For example, mercurous chloride with aqueous ammonia yields a black compound this again has been proved to be a mixture of finely divided mercury and mercuric chloroamidc. The reaction may be represented thus ... 

It has been found on examination of the ammino-derivatives of mercuric halides that the nature of the halogen present has a marked effect on the stability ol the compound. Thus, diammino-mercuric chloride, [Hg(NH3)2]Cl2, is stable and does not readily lose ammonia, whereas the corresponding iodide, diammino-mercuric iodide, [ITg (NH3) JI2, readily loses ammonia at ordinary temperature. The stability decreases in the order chloride, bromide, iodide. 

Ammino-mercuric Chlorides.—Six ammino-salts of mercuric chloride are known. These are monammino-mercunc chloride, [Hg(NH3)]Cl3 diammino-mercuric chloride, [Hg(NH3)2]Cl2 triammino-mercuric chloride, [FIg(NII3)3]Cl2 tetrammino-mercuric chloride, [Hg(NH3)4]Cl2 triammino-dimercuric chloride, [Hg2(NH3)3]Cl4 5 and dodecammino-mercuric chloride, HgC]2.12NII3. This last derivative is only stable if kept under pressure, and if pressure is released ammonolysis takes place in accordance with the equation... 

The best known and most important compound belonging to the ammino-mercurie salts is the so-called fusible precipitate of composition HgCl2.2NH3, diammino-mercuric chloride. It was originally represented as a double salt of dimercuriammonium chloride and ammonium cliloride, Hg2NCl.NH4Cl, but this has been proved to be incorrect, and the addition formula is now accepted as the one which bears out its chemical behaviour. 

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 ... 

Two ammino-derivatives of titanic chloride, namely, octammino-titanic chloride, [Ti(NH3)8]Cl4, and hewammino-titanic chloride, [Ti(NH3)6]Cl4, are described.1... 

Ammino - derivatives of Stannous Chloride.—The composition of the additive compounds of stannous chloride and ammonia varies with the temperature at which the substances are caused to combine.2... 

Diammino-stannous Chloride, [Sn(NH3)2]Cl2.—If dry ammonia gas is passed over anhydrous stannous chloride, immersed in a freezing mixture, a yellow powder is formed of composition SnCl2.2NH3. It blackens on exposure to light, and moist air attacks the substance, with formation of stannous oxide and ammonium chloride. If absorption is allowed to take place at ordinary temperature a mixture of mon-ammino-stannous chloride, [Sn(NH3)]Cl2, and diammino-stannous chloride, [Sn(NH3)2]Cl2, is obtained whilst at 100° C. stannous chloride is claimed to absorb ammonia gas, with formation of a white powder of composition corresponding to monammino-stannous chloride, [Sn(NH3)]Cl 2. 

---