Platinum trichloride

PtCl2, and platiaum tetrachloride [37773-49-2]. Platiaum dichloride exists in an a- and P-form, the latter containing a Pt core and edge-bridging chlorides. Platinum trichloride [25909-39-1], PtCl, contains Pt(II) and Pt(IV) centers. Other haHdes include two bromides, PtBr2 [13455-12-4] and PtBr ... 

Platinum Trichloride, PtCl3, results3 when platinum tetrachloride is heated to 390 C. in a current of pure, dry chlorine for several hours. 

Platinum trichloride is prepared by heating PtCL in dry chlorine at 390°. It is readily soluble in tailing water, but may be hydrolyzed by continued boiling. The trichloride docs not dissolve in concentrated HC1, but when the mixture is warmed a reaction takes place, producing both PtCI2 and PtCl,. 

Phosgene can be employed in a variety of metal-recovery operations, eg, in the recovery of platinum, uranium, plutonium, and niobium (69—73). Phosgene has been proposed for the manufacture of aluminum chloride, beryllium chloride, and boron trichloride (74—76). Phosgene has been patented as a stabilizer, either by itself or in combination with thionyl chloride, for Hquid SO2 (77). 

For preparing organotin trichlorides by this route, the slowest step is the reaction of R2SnCl2 with SnCLr, and it has been shown that this reaction (and that of ILtSn) is catalyzed by platinum and palladium compounds, for example, Equation (127).329... 

Phosphorus Pentoxide Phosphorus Trichloride Platinic Acid, Hexachloro Platinum... 

Organic derivatives of phosphorus trichloride—i.e., chlorophosphines of the types RPC12 or R2PC1—had never been fluorinated. We assumed the hitherto unknown fluorophosphines to be possibly interesting ligands in coordination chemistry. Such expectations were supported by earlier observations of Chatt (5, 6) and Wilkinson (32), who found that the parent compound phosphorus trifluoride as a ligand in certain coordination compounds with platinum or nickel behaved very much like carbon monoxide. 

Platinum(II)15 and palladium(II)16 complexes of phosphorus trichloride undergo solvolysis in water and alcohols to form complexes with orthophosphorous acid or orthophosphite ligands (equation 6). Similar reactions occur between the palladium(II) phenyldichlorophosphine complex (8) and the diols ethyleneglycol and catechol, but new chelate rings are not formed (Scheme 2). Solvolysis also occurs with attack of diphenylphosphinic acid or a similar diphenylchlorophosphine complex (9) (equation 7). The palladium complexes (8) and (9) are unstable to excess methanol, water or base and undergo reduction. Similarly, the phosphorus trichloride gold(I) complex (10) is reduced by water, but forms stable products on reaction with alcohols (equation 8).15 During the above reactions, the phosphorus—metal bond remains intact and the overall process is one of substitution at phosphorus. 

Benzeneselenenyl trichloride, 27 Platinum-Titanium, 251 Titanium(IV) chloride-Zinc, 310 Dehydrohalogenation (see Elimination reactions)... 

Dibutylamine, piperidine, N-ethylcyclohexylamine, N-ethyldicyclohexylamine, and the ketones were reagent grade chemicals. The 5% palladium on carbon, 5% platinum on carbon, sulfided 5% platinum on carbon and sulfided 5% rhodium on carbon catalysts were obtained from Engelhard Industries. The 20% molybdenum sulfide on alumina (Girdler T-318) was obtained from the Chemetron Corp. Palladium chloride was obtained from Matheson, Coleman and Bell. Ruthenium trichloride was obtained from Ventron. 

Ruthenium trichloride catalyzes the production of oxygen at a platinum anode404 via higher oxidation state species, whilst one of the most effective catalysts for oxygen or chlorine evolution is formed by reduction of a solution containing [Fe2(S04)3] and K3[Ru(CN)6].404 This leads to a film on the electrode of ruthenium purple, Fe4[Ru(CN)6]3, with a structure analogous to that of Prussian blue. Oxygen can then be produced at 0.2 V vs. SCE.404... 

Tricyclohexylphosphine was obtained from Strem Chemicals. Ruthenium, rhodium, and iridium trichlorides were obtained as trihydrates from Johnson, Matthey Limited. Iridium tetrachloride was obtained from Platinum Chemicals. The precursor complexes [RhCl(COD)]2 (57), [RhCl(COT)2]2 (58), [RhCl(C2H4)2]2 (59), [IrCl(COD)]2 (14), and [HIrCl2-(COD)]2 (31) were made according to the literature procedures. 

The reaction of a molten mixture of 3,4-dihydro-2//-pyrido[ 1,2-a] pyrimidin-2-one 675 and phosphorous acid with phosphorus trichloride, followed by treatment of the reaction mixture with 2 N aqueous hydrochloric acid, afforded 3,4-dihydropyridopyrimidine-2,2-diphosphoric acid 676 in 38% yield (91GEP3930130). Catalytic reduction of diphosphonic acid 676 in water over platinum dioxide gave hexahydropyrido[l,2-a]pyrimi-dine-2,2-diphosphonic acid 677. 

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. 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

Chemical Properties.—Iridium is not attacked by fluorine in the cold, but on warming to dull redness, vapours of the fluoride are evolved.7 Also, when employed as anode in the preparation of fluorine,8 it is rapidly attacked. Chlorine at red heat unites with iridium to form the trichloride a mixture of chlorine and carbon monoxide at 240° C. has no action on the metal9 although platinum is attacked by it. 

The trichloride is almost insoluble in concentrated hydrochloric add at room temperature, but on warming the two, decomposition takes place, the di- and tetra-chlorides of platinum resulting. 

Hydrated Platinum Sesquioxide, Pt203.a H30, may be obtained 7 by decomposing the trichloride, PtCla, with a hot solution of sodium... 

Various compounds of platinum dichloride with phosphorus trichloride and with phosphorous acid have been prepared.5... 

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