Chlorostannate

HjSnCl, with which the aniline forms a salt, aniline chlorostannate (C4HjNH )i,H SnCl4, similar in type to aniline chloroplatinate (p. 448). The crude product is therefore made strongly alkaline with sodium hydroxide, which liberates the base with the formation of sodium stannate, and the aniline can (C4H NH,),H,SnCl, + SNaOH = 2C,H,NH, + Na.SnO, +6NaCl + sHjO then be removed by steam-distillation. 

Other studies of the toxicity of stannous fluoride, sodium pentafluorostannite, sodium pentachlorostannite, sodium chlorostannate, stannous sulfide [1314-95-0] stannous and stannic oxides, stannous pyrophosphate [15578-26 ] stannous tartrate [815-85-0] and other inorganic tin compounds are reviewed in References (dh—12. The OSHA TLV standard for inorganic tin compounds is two milligrams of inorganic tin compounds as tin per cubic meter of air averaged over an eight-hour work shift (47). 

Ammonium-ferrisulfat, n. ammonium iron(III). sulfate, ferric ammonium sulfate, -ferro-sulfat, n. ammonium iron(II) sulfate, ferrous ammonium sulfate, -jodat, n. ammonium iodate. -jodid, n. ammonium iodide, -platinchlorid, n. ammonium platinichloride (chloroplatinate). -rest, m. ammonium radical. rhodanid, -rhodantir, n. ammonium thiocyanate, -salpeter, m. ammonium nitrate, -salz, n. ammonium s t. -selfe,/. ammonia soap, -sulfhydrat, n. ammonium hydrosulfide, -sulfocyanid, n. ammonium thiocyanate, -verbindung,/. ammonium compound, -zinn-chlorid, n. ammonium chlorostannate, pink salt. 

Stannj.. stannic, stanni-. tin(IV). -azetat, n. stannic acetate, tin(IV) acetate, -chlorid, n. stannic chloride, tin(IV) chloride, -chlor-wasserstoffsaure, /. chlorostannic acid, -hydroxyd, n. stannic hydroxide, tin(IV) hydroxide, -jodid, n. stannic iodide, tin (IV) iodide. 

Zinn-bromwasserstoffsaure, /. bromostannic acid, -butter, /. (Old Chem.) butter of tin (stannic chloride), -charge, /. (Textiles) tin weighting, -chlorammonium, n. ammonium chlorostannate, (Dyeing) pink salt, -chlorid, n. tin chloride, specif, stannic chloride, tin (IV) chloride, -chloriir, n. stannous chloride, tin(II) chloride. 

Zinn-chlorwasserstoffsaure, /. chlorostannic acid, -diphenylchlorid, n. diphenyltin chloride. -Hiraht, m. tin wire. 

The ability of iron(III) chloride genuinely to catalyze Friedel-Crafts acylation reactions has also been recognized by Holderich and co-workers [97]. By immobilizing the ionic liquid [BMIM]Cl/FeCl3 on a solid support, Holderich was able to acetylate mesitylene, anisole, and m-xylene with acetyl chloride in excellent yield. The performance of the iron-based ionic liquid was then compared with that of the corresponding chlorostannate(II) and chloroaluminate(III) ionic liquids. The results are given in Scheme 5.1-67 and Table 5.1-5. As can be seen, the iron catalyst gave superior results to the aluminium- or tin-based catalysts. The reactions were also carried out in the gas phase at between 200 and 300 °C. The acetylation reac-... 

Ionic liquids formed by treatment of a halide salt with a Lewis acid (such as chloro-aluminate or chlorostannate melts) generally act both as solvent and as co-catalyst in transition metal catalysis. The reason for this is that the Lewis acidity or basicity, which is always present (at least latently), results in strong interactions with the catalyst complex. In many cases, the Lewis acidity of an ionic liquid is used to convert the neutral catalyst precursor into the corresponding cationic active form. The activation of Cp2TiCl2 [26] and (ligand)2NiCl2 [27] in acidic chloroaluminate melts and the activation of (PR3)2PtCl2 in chlorostannate melts [28] are examples of this land of activation (Eqs. 5.2-1, 5.2-2, and 5.2-3). 

As early as 1972 Parshall described the platinum-catalyzed hydroformylation of ethene in tetraethylammonium trichlorostannate melts [1]. [NEt4][SnCl3], the ionic liquid used for these investigations, has a melting point of 78 °C. Recently, platinum-catalyzed hydroformylation in the room-temperature chlorostannate ionic liquid [BMIM]Cl/SnCl2 was studied in the author s group. The hydroformylation of 1-octene was carried out with remarkable n/iso selectivities (Scheme 5.2-13) [66]. 

Despite the limited solubility of 1-octene in the ionic catalyst phase, a remarkable activity of the platinum catalyst was achieved [turnover frequency (TOP) = 126 h ]. However, the system has to be carefully optimized to avoid significant formation of hydrogenated by-product. Detailed studies to identify the best reaction conditions revealed that, in the chlorostannate ionic liquid [BMIM]Cl/SnCl2 [X(SnCl2) = 0.55],... 

Moreover, these experiments reveal some unique properties of the chlorostan-nate ionic liquids. In contrast to other known ionic liquids, the chlorostannate system combine a certain Lewis acidity with high compatibility to functional groups. The first resulted, in the hydroformylation of 1-octene, in the activation of (PPli3)2PtCl2 by a Lewis acid-base reaction with the acidic ionic liquid medium. The high compatibility to functional groups was demonstrated by the catalytic reaction in the presence of CO and hydroformylation products. 

In other crystals an octahedral metal atom is attached to six non-metal atoms, each of which forms one, two, or three, rather than four, bonds with other atoms. The interatomic distance in such a crystal should be equal to the sum of the octahedral radius of the metal atom and the normal-valence radius (Table VI) of the non-metal atom. This is found to be true for many crystals with the potassium chlorostannate (H 61) and cadmium iodide (C 6) structures (Table XIB). Data are included in Table XIC for crystals in which a tetrahedral atom is bonded to a non-metal atom with two or three covalent bonds. The values of dcalc are obtained by adding the tetrahedral radius for the former to the normal-valence radius for the latter atom. 

Chlorostannate ionic liquids have been used in hydroformylation reactions [23], Acidic [bmimjCl-SnCb and [l-butyl-4-methylpyridinium]Cl-SnCl2 were prepared from mixing the respective [cation]+ Cl with tin(II)chloride in a ratio of 100 104, much in the same way that the chloroaluminates are made (see Chapter 4). Both these chlorostannate ionic liquids melt below 25 °C. Addition of Pd(PPh3)2Cl2 to these chlorostannate ionic liquids leads to a reaction medium that catalyses the hydroformylation of alkenes such as methyl-3-pentenoate as shown in Scheme 8.9. The ionic liquid-palladium catalyst solution is more effective than the corresponding homogeneous dichloromethane-palladium catalyst solution. The product was readily separated from the ionic liquid by distillation under vacuum. This is an important reaction as it provides a clean route to adipic acid. 

Rubidium also may be recovered by the chlorostannate method. In this method the alkali metal carbonate solution obtained from the mixed alum is treated with carbon dioxide. Most potassium is precipitated as bicarbonate, KHCO3. Addition of hydrochloric acid converts the carbonates to chlorides. The chlorides are converted to chlorostannates by carefully adding stoichiometric quantities of stannic chloride at pH just below 7 ... 

Cesium chlorostannate, Cs2SnCl6, more insoluble than the rubidium salt, precipitates before any rubidium starts to precipitate. Under such controlled addition of stannic chloride, potassium chloride remains in solution in chloride form. Rubidium chlorostannate complex, on thermal decomposition, forms rubidium chloride, RbCl. 

Preparation of Chlorostannic Acid. Pour concentrated hydrochloric acid into tin(IV) chloride in a proportion of 28 parts by mass of hydrogen choride to 100 parts by mass of the tin chloride. Cool the solution and pass a stream of dry hydrogen chloride into it until its absorption stops. Test the reaction of chlorostannic acid with... 

Preparation of Ammonium Chlorostannate. Prepare a 60% tin(IV) chloride solution in concentrated hydrochloric acid and add to it a warm saturated solution containing an equimolecular amount of ammonium chloride. Cool the solution with a mixture of ice and sodium chloride, filter off the crystalline precipitate using a glass filter No. 3, and wash the precipitate on the filter with the smallest possible amount of concentrated hydrochloric acid cooled to 0 °C. 

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