Platinum chloride ethylene complex

Flynn and Hulburt, however, went further into a study of the hydrogenation of ethylene by hydrogen when a stream of these gases was passed through a solution of ethylene platinum chloride. They found that ethylene inhibits the formation of platinum metal. This inhibition seems to indicate that the first step of the reduction is a dissociation of the complex with ethylene as one of its products. The platinum formed as a result of the initial dissociation and reduction would catalyze the reduction of the complex. Ethylene, however, still inhibits the reaction markedly in the presence of platinum. 

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 predominant photoreaction of the [Pt(C2H4)Cl3] anion is loss of ethylene, which is accompanied by a little loss of m-chloride. This behaviour contrasts with the corresponding thermal reaction, where the predominant reaction is loss of the chloride trans to the ethylene. This contrast between thermal and photochemical behaviour is novel most photochemical reactions of platinum(ii) complexes follow the same course as the corresponding thermal reactions, but occur more quickly. The photoaquation of the ethylene ligand is subject to sensitization by acetone or by acetophenone, and therefore probably occurs via the first excited singlet state. A general model for photosubstitution reactions has been described, which is relevant to octahedral as well as to square-planar complexes. ... 

My last comment concerns the reaction of palladium olefin complexes with carbon monoxide discovered by Tsuji. I agree that this is most likely to proceed by an insertion rather than an ionic mechanism. Chloride attack on coordinated olefin is rare however. Chloride ion is an inhibitor, for example in the palladous chloride catalyzed hydration of ethylene (0). I, therefore, wondered whether carbon monoxide was affecting the ease with which chloride attacks olefin. One can postulate that carbon monoxide participates in this insertion either as a gas phase reactant or by first forming a carbonyl olefin complex. Such complexes of the noble metals were unknown, but examining the reaction between carbon monoxide and the halogen bridged olefin complexes of platinum revealed that they are formed very readily... 

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. 

Among the most significant developments in the field of catalysis in recent years have been the discovery and elucidation of various new, and often novel, catalytic reactions of transition metal ions and coordination compounds 13, 34). Examples of such reactions are the hydrogenation of olefins catalyzed by complexes of ruthenium (36), rhodium (61), cobalt (52), platinum (3, 26, 81), and other metals the hydroformylation of olefins catalyzed by complexes of cobalt or rhodium (Oxo process) (6, 46, 62) the dimerization of ethylene (i, 23) and polymerization of dienes (15, 64, 65) catalyzed by complexes of rhodium double-bond migration in olefins catalyzed by complexes of rhodium (24,42), palladium (42), cobalt (67), platinum (3, 5, 26, 81), and other metals (27) the oxidation of olefins to aldehydes, ketones, and vinyl esters, catalyzed by palladium chloride (Wacker process) (47, 48, 49,... 

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°. 

ABSOLUTE ALCOHOL or ABSOLUTE ETHANOL (64-17-5) Forms explosive mixture with air (flash point 55°F/13°C). Reacts, possibly violently, with strong oxidizers, bases, acetic anhydride, acetyl bromide, acetyl chloride, aliphatic amines, bromine pentafluoride, calcium oxide, cesium oxide, chloryl perchlorate, disulfuryl difluoride, ethylene glycol methyl ether. Iodine heptafluoride, isocyanates, nitrosyl perchlorate, perchlorates, platinum, potassium- er -butoxide, potassium, potassium oxide, potassium peroxide, phosphonis(III) oxide, silver nitrate, silver oxide, sulfuric acid, oleum, sodium, sodium hydrazide, sodium peroxide, sulfmyl cyanamide, tetrachlorosilane, i-triazine-2,4,6-triol, triethoxydialuminum tribromide, triethylaluminum, uranium fluoride, xenon tetrafluoride. Mixture with mercury nitrate(II) forms explosive mercury fulminate. Forms explosive complexes with perchlorates, magnesium perchlorate (forms ethyl perchlorate), silver perchlorate. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

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