Palladium chloride PdCl

PdCl(7r-C3H5)]2 is reported to exist in two forms (163), i.e., the yellow or a-form described above, and a dark green or /3-form prepared by reacting palladium chloride with an acidified aqueous solution of allyl alcohol below 10° at 15° the product is the yellow a-form (163). Isomerization of this type has not been reported for other 7r-allylicpalladium complexes. 

A mixture of palladium chloride and triphenylphosphine effectively catalyzes carboxylation of linoleic and linolenic acids and their methyl esters with water at 110°-140°C and carbon monoxide at 4000 psig. The main products are 1,3-and 1,4-dicarboxy acids from dienes and tricarboxy acids from trienes. Other products include unsaturated monocar-boxy and dicarboxy acids, carbomethoxy esters, and substituted a,J3-unsaturated cyclic ketones. The mechanism postulated for dicarboxylation involves cyclic unsaturated acylr-PdCl-PhsP complexes. These intermediates control double bond isomerization and the position of the second carboxyl group. This mechanism is consistent with our finding of double bond isomerization in polyenes and not in monoenes. A 1,3-hydrogen shift process for double bond isomerization in polyenes is also consistent with the data. 

Palladium Chloride. Paliadous chloride. Cl2Pd mol wt 177.30. Cl 39 997c, Pd 60.01%. PdCl,. Prepn Krustinsons, Z. Eiektrochem. 44, 537 (1938). Review of PdClj and other halides J. H. Canterford, R. Colton, Halides of the Second and Third Row Transition Metals (John Wiley, New York, 1968) pp 358-389. 

CAS 7647-10-1 EINECS/ELINCS 231-596-2 Synonyms Palladium chloride Palladium (2+) chloride Palladium chloride anhydrous Palladium (II) chloride anhydrous Palladium dichloride Palladous chloride Classification Halide Empirical CLPd Formula PdCL... 

PdCl. C LiJPdClJ Palladium chloride complexes 7i-Allylpalladium chloride complex [PdCl fCHsCNk], lPdCk(C,H,CN)J... 

Palladium chloride supported on silica gel and "y-alumina are active for the dimerization of ethylene [252]. PdCl2(Me2SO)2 and K PdCl,(MeSO) on KSH-2 silica gel catalyze ethylene dimerization. The yield of dimer and selectivity are high with use of 0.1% dimethylsulfoxide complex precipitated from acetone at 90°C and with 0.3% ionic complex precipitated from chlorobenzene at 100°C [252-255]. 

Very recently, well-defined complexes with general formula [PdCl(T -Cp) (NHC)] were synthesised and tested for the homocoupling of non-electrodeficient arylboronic acids at room temperature with good results (Scheme 7.7) [51]- This new class of catalysts were synthesised from commercially available NHC palladium(II) chloride dimers and are air-stable. 

Palladium dichloride forms polymeric carhonyl complexes when the dry chloride is heated in a stream of carhon monoxide charged with methane vapor. Such complexes include [PdCl2(CO)n] and [PdCl(CO)2]n. The reaction also occurs in aqueous phase resulting in decolorization of the solution. 

When ammonia gas is passed through an aqueous solution of PdCL, the product is tetrammine palladium(II) chloride, Pd(NH4)2Cl2. The same product also is obtained in dry state by passing ammonia gas over anhydrous PdCL. 

The first member of the chloro-bridged series di-M-chlorodi-ir-allyldi-palladium, [PdCl(Tr-C3H6)]2 is conveniently prepared by treating allyl alcohol (162, 168, 194) or allyl chloride (121, 122, 123) with palladium... 

Diphenylacetylene and methylphenylacetylene react with palladium halides to give a very interesting series of compounds some of which are almost certainly ir-allylicpalladium complexes. Thus diphenylacetylene (ChHjo) reacts with palladium(II) chloride in ethanol to give hexaphenyl-benzene and a complex of the composition [PdCl(Ci4Hi0)2(OC2H6)] 148, 149) which we formulate as the ir-allylic complex (XLVI) (see Section... 

The 7r-allylpalladium complex [PdCl(7r-C iH6)]2 on heating decomposes quantitatively into allyl chloride and palladium. The analogous ir-meth-allylpalladium complex gives a 96% yield of methallyl chloride but a little isobutene is also formed 123). 

Palladium appears to be especially suitable for forming these complexes. As an example, allyl alcohol reacts with palladium (II) chloride (236) to give bis(allylpalladium chloride), [(C3H6)PdCl]2. Its nmr spectrum shows three peaks (56), in the ratio 1 2 2, indicating the structure shown in Fig. 20. The exact location of the allyl groups with respect to the metal... 

Dickinson s X-ray diffraction proof of a sqnare-planar arrangement of chloride ions around the central metal atoms in K2[PtCl4], K2[PdCL ], and (NFt4)2[PdCLi] (see Section 5.5.2) was confirmed by additional X-ray structural studies of other compounds. Linus Pauling explained the sqnare-planar structure of platinum(ll) and palladium(ll) compounds on a theoretical basis and predicted a similar configuration for diamagnetic compounds ofnickel(ll), gold(lll), copper(lll), and silver(lll). 

Other one-phase preparations of bimetallic nanoparticles include NOct4(BHEt3) (Oct = octyl, Et = ethyl) reduction of platinum and ruthenium chlorides to give Pt/Ru(l/1) nanoparticles by Bonnemann et al. [102-104], sono-chemical reduction of gold and palladium ions to provide Au/Pd nanoparticles by Mizukoshi et al. [105,106], and NaBH4 reduction of PtCl - and PdCl - dendrimer complexes to give dendrimer-stabilized Pd/Pt nanoparticles by Crooks et al. [107]. 

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