Platinum IV Chloride

Platini-, platinic, platini-, platinum (IV). -chlorid, n. platinic chloride, platinum (IV) chloride, -chlorwasserstoff, m., -chlorwasserstoffsaure, /. chloroplatinic acid, chloroplatinic (IV) acid, -cyanwasserstoffsaure, /. cyanoplatinic acid, cyanoplatinic(IV) acid, platinicyanic acid. 

The preparation of iodo (trimethyl) platinum (IV) of empirical formula PtI(CH3)3 was first reported by Pope and Peachey.1 The substance was produced by the reaction between platinum (IV) chloride and methylmagnesium iodide. Gilman et al.2 have repeated this method of preparation to give a 45% yield and have identified some of the side products of the reaction. Various starting materials and procedures have been used by... 

The analogous hydroxylation of alkynes to produce ketones is enhanced by the co-catalytic effect of Aliquat and platinum(IV) chloride-carbon monoxide [3] it is assumed that HPtCI(CO) is the active hydration species. C-S and C-Br bonds are cleaved under the reaction conditions. 

Formula PtCE MW 336.89 also forms a pentahydrate, PtCE 5H2O Synonyms platinum(IV) chloride platinic chloride... 

A small portion of the product is tested for any unreacted platinum(IV) chloride by leaching with a few drops of hot water. An equal volume of a saturated solution of ammonium chloride is added to the leach water, and if there is no precipitate within 1 minute the product is pure. If a precipitate appears, the entire product should be leached with water until free of the soluble platinum(IY) chloride. The purified product is partially dried by suction filtration and finally completely dried by a drying agent in a desiccator. The yield is 2.8 g. (91% based on H2PtCl6-6H20). Anal. Calcd. for PtCl2 Pt, 73.3 Cl, 26.6. Found Pt, 73.0 Cl, 26.8. ... 

Platinous compounds [see specific compounds under Platinum (II)] Platinum (II) chloride, 5 208 6 209 analysis of, 5 209 Platinum (IV) chloride, 2 253 Platinum (II) complex compounds, anions, with 1,4-butadiene, K2[Cl3PtC4H6PtCI3], 6 216 anions, with ethylene, [Pt(C2H4)-CU]K, 5 211, 214... 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

Macyk W, Burgeth G, Kisch H. Photoelectrochemical properties of platinum(IV)-chloride surface modified Ti02. Photochem Photobiol Sci 2003 2 322-8. 

Macyk W, Kisch H. Mechanism of titanium dioxide photosensitization by platinum(IV)chloride surface complexes. / Inf Rec 2000 25 435-8. 

Janczyk A, Wolnicka-Glubisz A, Urbanska A, Stochel G, Macyk W. Photocytotoxicity of platinum(IV)-chloride surface modified Ti02 irradiated with visible light against murine macrophages. J Photochem Photobiol B Biol 2008 92 54-8. 

Macyk W, Kisch H. Photosensitization of crystalline and amorphous titanium dioxide by platinum(IV) chloride surface complexes. Chem Ear J 2001 7 1862-7. 

Zang L, Lange C, Maier WF, Abraham I, Storck S, Kisch H. Amorphous microporous titania modified with platinum(IV) chloride - a new type of hybrid photocatalyst for visible light detoxification. J Phys Chem B 1998 102 10765. 

Commonly accepted mechanisms of the MMO reactions are based on the concept of the activation of dioxygen or the use of shunts such as H202. Nevertheless, the new mechanism of methane oxidation via an intermediate complex containing pentacoordinated carbon has been forwarded (Shilov, 1997, Karasevich et al 1998, 1999). This suggestion is based on experiments on the multiple H-D exchange and methane oxidation catalyzed by platinum (II) complexes, ([H2PtCl6], for instance). Formation of methyl platinum (IV) chloride complex in methane oxidation was confirmed by its NMR spectrum. 

Di-jj-chloro-dichlorobis(ethylene)diplatinum(II) is customarily prepared by evaporating an aqueous solution of H[PtCl3(C2H4)] to dryness and then recrystallizing the dimer.1 However, this procedure has not been applied as a general synthesis of other related olefin complexes. The dimer has also been prepared, but with less success, by the reaction of Na2PtCl6 with boiling ethanol.2 The direct reaction of ethylene with platinum(IV) chloride also provides the dimer,3 but yield data are not available and presumably the method is unsatisfactory. 

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... 

Tris(ethylenediamine)pIatinum(IV) chloride was first reported by A. Werner in 1917. Several variations of his method have been used, but basically the preparation from platinum involves three steps (1) the preparation of the hexachloroplatinic(IV) acid, (2) the preparation of the crude tris(ethylenediamine)platinum(IV) chloride, and (3) purification. The following procedure is a modification of Werner s method. 

Preparation of Crude Tris(ethylenediamine)platinum(IV) Chloride. Ten and one-tenths grams (0.019 mol, assuming the 6-hydrate) of hexachloroplatinic(IV) acid is dissolved in 80 ml. of absolute ethanol. After cooling this solution in an ice bath, 6.6 ml. of 98% ethylenediamine [5 mols of ethyl-enediamine per mol of hexachloroplatinic(IV) acid] is slowly added with constant stirring. A pale yellow precipitate forms immediately. The mixture is heated to 65° and is maintained at 65 1° in a water bath for 2 hours. Care must be exercised not to heat the reaction mixture above 70° inasmuch as a brown gum occasionally forms at higher temperatures. The mixture is stirred constantly during the digestion period. Absolute ethanol is added as required to keep the volume of the reaction mixture constant. The mixture is allowed to cool to room temperature, and the tris(ethylenediamine)platinum(IV) chloride is separated from the ethanol solution by suction filtration. The crude yellow product is washed twice with absolute ethanol. The yield of the crude wet product is about 17 g. 

Tris(ethylenediamine)platinum(IV) chloride is a white crystalline solid which is readily soluble in water and stable toward decomposition in both acidic and basic solution. Resolution of the complex cation into its optical isomers has been achieved by fractional precipitation of i-[Pt(en)3]-Cl2(d-C4H406) on addition of ammonium d-tartrate to the racemic mixture. Racemization of the cation occurs only under extreme conditions and is accompanied by little exchange of bound ethylenediamine. A solution of the complex is quantitatively reduced to platinum metal by magnesium and hydrochloric acid. The solid complex is quantitatively reduced to platinum metal upon ignition. 

The reaction vessel is a 125-mL filter flask with a white rubber pipette bulb wired onto the side arm (Fig. 1). Introduce 10 mL of water, 1 mL of platinum(IV) chloride solution, and 0.5 g of decolorizing charcoal and swirl during addition of 3 mL of stabilized 1 M sodium borohydride solu-... 

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