Ethylene platinous chloride

The gaseous products formed on thermal decomposition of ethylene-platinous chloride are ethylene, hydrogen chloride, vinyl chloride, ethyl chloride, ethylene dichloride and ethylidine dichloride. The half life for the decomposition at 130° is 4.5 days, at 172° it is 1.7 hours 98). The hydrolysis of Zeisc s salt K[PtCl3(C2H4)] by water and dilute acids has been studied ... 

The only problem remaining in formulating say, ethylene platinous chloride (VI), was how the olefin attached itself to the transition metal atom. There were reports of ill-defined zinc- and aluminum-olefin complexes, and most chemists, if they thought of them at all, believed that olefin compounds, though much less stable and less numerous than the ammines, occurred just as widely. 

Cope and co-workers resolved ( )-trani-cyclooctene (1) by reaction with the complex (2) from ethylene, platinous chloride, and (4-)-l-phenyl-2-aminopropane. 

Resolution 3t3-Acetoxy-A. etienic add. T-Acid from a tetranitrofluorenone and an optically active hydroxylamine. i><—>Butane-2,3-diol. L.(+)-Butane-2,3-dithiol. (By crystallization Silver acetate). 10-Camphorsulfonic acid. 10-Camphorsulfonyl chloride. 4-(4-Carboxy-phenyl) semicarbazide. Complex from ethylene, platinous chloride, and (- -)-l-phenyi-2-aminopropane. Debydroataetylamine. Diisopinocampheylborane. Di-p-toluoyl-o-tartrate. d- and /-u-Phenylethylamiiie. L-Pyrrolidonecarboxylic add. a-(2,4,S,7-Tetianitro-9-fluorenyl-ideneaminooxy)-propionic acids. 

Zeise s salt. (Pt(C2H4)Cl3)K. Formed by adding potassium chloride to a solution of platinous chloride saturated with ethylene. 

Use for resolution of cycloalkenes. W s-Cycloalkenes of intermediate size (Cg-Cjo) should be capable of existing in enantiomeric forms because of the inability of the trans double bond to rotate with respect to the remainder of the molecule. But in the absence of salt-forming groups, resolution cannot be accomplished by the usual methods of forming derivatives. However, Cope et al.s found that the strong tendency of an alkene to complex with a platinum compound provides an effective method of resolution. The complex of ethylene with platinous chloride and (+) or (-)-a-methylbenzylamine exists in only one form since ethylene is symmetrical. But addition of the base to a solution of the platinum complex of trans-cyclooctene opens the way for formation of the diastereoisomeric complexes derived from the R- and S-forms of the base. Fractional crystallization at —20° (liquid at 25°) effected separation. Liberation of the (—)-hydrocarbon from the complex with potassium cyanide gave a product of aD — 411°. 

It is probable that tetrachloro(diethyIene)diplatinum(II) was first prepared by Zeise by decomposition of trichloro-(ethylene)platinic(II) acid.1 Boiling hexachloroplatinic-(IV) acid with chloroform also gave the compound.2 However, it was first obtained in sufficient quantity for investigation by Anderson,3 who boiled an ethanolic solution of sodium hexachloroplatinate(IV) 6-hydrate until reduction to platinum(II) was complete. This procedure is tedious, and the yields are affected markedly by impurities in the platinum salt and by the presence of other platinum metals.4 Optimum yields of 75% are obtained only after much experience. The general method of Kharasch and Ashford,5 involving adding an olefin to a suspension of platinum(IV) chloride in warm benzene or glacial acetic... 

This is about 100% in excess of the theoretical quantity required for precipitating all of the potassium in potassium trichloro(ethylene)platinic(II) acid as the chloride. 

Trichloro(ethylene)platinate(II) ion is formed by reaction with aqueous chloride solutions8... 

In a further discussion of the constitution of alcohol and ether Liebig attacked Dumas etherin theory (see p. 343) and defended the ethyl theory. He also attacked Dumas substitution theory in its application to the formation of chloral (see p. 361). Dumas views, Liebig said, were founded on inexact experiments and he remained silent when his errors were pointed out to him. We should be ready at every moment to change admitted hypotheses for better theories. Since Zeise s compound of platinous chloride and ethylene seemed to support the etherin theory, Liebig recalculated Zeise s analyses to show that the compound contains oxygen and is a compound of ether and not ethylene (etherin). Zeise confirmed that the compound does not contain oxygen. 

Xanthic acid was investigated by Couerbe. Zeise discovered thiocarbamic acid by the action of carbon disulphide on ammonia, the addition compound of ethylene and platinous chloride (Gekohltenwasserstoffes Chlorplatin), and mercaptan (from corpus mercurium captans), by distilling potassium hydrosulphide with potassium ethyl sulphate KKS +0211 0—... 

The ethylene oxide bases (bases oxyethyleniques) obtained by Wurtz by the action of aqueous ammonia on ethylene oxide, and now formulated NH2(C2H4),iO,j iOH, were of some interest in relation to the synthesis of choline, discovered in bile (xoA ) by Strecker. He prepared a compound with platinic chloride which he formulated C5H14NOCI, PtCl —... 

The first explicit information appeared in 1953 in two U.S. patents (9) which showed that platinum black as well as platinized asbestos or silica were effective for addition of trichlorosilane to olefins. Platinum on charcoal was unusually active with trichlorosilane and acetylene, ethylene, butadiene, vinyl chloride, or vinylidene fluoride. Temperatures as low as 130°C were sometimes employed. 

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... 

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