Palladium II

Palmer and have carried out extensive investigations into the 

Substitution reactions of [Pd(L-L)Cl2] [Table 4.3(d)] obey the usual two-term rate law for replacement of the first chloride (the second chloride is replaced rapidly). The discriminating abilities of these complexes (calculated from pd values obtained using the standard substrate rra 5-[Pd(PR3)2(N02)2]) increase with decreasing of the ligand (L-L) and, as in the case of some Pt(II) complexes, the behavior of thiourea as entering group is anomalous. 

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In a lOOmL round-bottomed flask fitted with a magnetic stirrer is placed a mixture of palladium (II) chloride (89mg, O.Smmol), p-benzoquinone (5.94g, 55mmol) and 7 1 dimethylformamide/water (20mL). To the solution, t-decene [substitute safrole for this compound) (7.0g, 50mmc4) is added in 10 min and the mixture is stirred at room temperature for 7h. The solution is poured into cold 3 normal hydrochloric acid (lOOmL) and extracted with 5 portions of ether. The extracts are combined and washed with three portions of 10% aqueous sodium hydroxide solution and a portion of brine, and then dried After removal of the solvent, the residue is distilled to give 2-decanone [P2P] yield 6.1g (78%). 

Example 68 Add. 1 mole of 3-(3,4-methylenedioxyphenyl) propylene,. 25 mole of methyl nitrite,, 5L of methanol, 36g of water,. 006 mole of bisfbenzonitrile) palladium (II) chloride as a catalyst to a flask. Stir magnetically for 1.5 hours at 25C. The conversion of the starting material was 100%, the yield of MDP-2-P was 88%. 

Chloro(tris[2-(dimethylamino)ethyl]amine) palladium(II) [66632-97-1]... 

It has been discovered that styrene forms a linear alternating copolymer with carbon monoxide using palladium II—phenanthroline complexes. The polymers are syndiotactic and have a crystalline melting point - 280° C (59). Shell Oil Company is commercializing carbon monoxide a-olefin plastics based on this technology (60). 

As foretold in the introduction, ring formation via attack on a double bond in the endo-trig mode is not well exemplified. The palladium(II) catalyzed oxidative cyclization of o-aminostyrenes to indoles has been described (78JA5800). The treatment of o-methyl-selenocinnamates with bromine in pyridine gives excellent yields of benzoselenophene-2-carboxylates (Scheme 10a) (77BSF157). The base promoted conversion of dienoic thioamides to 2-aminothiophenes is another synthetically useful example of this type (Scheme 10b) (73RTC1331). 

Consequent potentiometric titration of osmium(IV) and laithenium (IV) in their mixtures has been canied out in broad range of concentrations from 1 mkg to 200 mkg in samples of 20 ml. It has been shown the possibility of amperemetric determination of osmium(VI) in binary and triple systems with silver(I), platinum(IV), palladium(II), gold(III), founded on formation of corresponding compounds with dimerkaptotiopiron, having a different solubility. The deteriuination of Os(VI) is possible under tenfold - hundredfold excess of above mentioned metals. 

COMPARATIVE SORPTION OF GOLD(III), PLATINUM(IV) AND PALLADIUM(II) ON VARIOUS ORGANOPOLYMERIC... 

We have conducted the comparative study of gold (III), platinum (IV) and palladium (II) acidocomplexes solution on macroporous granular sorbents on the basis of polystyrene with functional groups of methyleneamine, 3-methylpyrasolyl, N,N-dimethylaminomethylene, dimethylmethylene-P-oxyethylamine and with functional 6-(3-methylpyridine) groups on polyvinylpyridine basis as well as fibrous polystyrene sorbent with pyrazolyl groups. 

Gold (III) and palladium (II) are sorbed quantitatively on all studied sorbents, except for methyleneamine, from solutions 0,2-2 M HCI. The degree of platinum (IV) complex extraction substantially depends not only on the nature of sorbent functional groups, but also on geometrical parameters of the matrix. This factor influences gold (III) and palladium (II) soi ption to a lesser extent. 

Palladium (II) chloride [7647-10-1 ] M 177.3, m 678-680". The anhydrous salt is insoluble in H2O and dissolves in HCl with difficulty. The dihydrate forms red hygroscopic crystals that are readily reduced to Pd. Dissolve in cone HCl through which dry CI2 was bubbled. Filter this solution which contains H2PdCl4 and H2PdCl6 and on evaporation yields a residue of pure PdQ2. [Handbook of Preparative Inorganic Chemistry (EdBrauer) Vol 2 1582 7965 Org Synth Coll Vol III 685 1955.]... 

Palladium (II) trifluoroacetate [42I96-3I-6] M 332.4, m 210"(dec). Suspend in trifluoroacetic acid and evaporate on a steam bath a couple of times. The residue is then dried in vacuum (40-80°) to a brown powder. [J Chem Soc 3632 7965 J Am Chem Soc 102 3572 1980.]... 

A mechanism for alkene arylation by palladium(II) is given below. The isotope effect was found to be 5 when benzene-dg was used. When styrene-/S,i5-d2 was used. 

Diacetato(l, 10-phenanthroline)palladium(II)-catalyzed transetheriflcation of polyfluorinated alcohols with enol ethers leads to the corresponding fluormated vinylic ethers [14] (equation 13)... 

Bis(benzonitrile)palladium(II) chloride, benzene, reflux, 16-20 h, 86% yield. 

Hydrogen is a colourless, tasteless, odourless gas which has only low solubility in liquid solvents. It is comparatively unreactive at room temperature though it combines with fluorine even in the dark and readily reduces aqueous solutions of palladium(II) chloride ... 

The Hegedus indole synthesis involves one of the earlier (formal) examples of olefin hydroamination. An ortho-vinyl or ortho-nllyl aniline derivative 1 is treated with palladium(II) to deliver an intermediate resulting from alkene aminopalladation. Subsequent reduction and/or isomerization steps then provide the indoline or indole unit 2, respectively. 

The classical tiaP) complexes were basically described for the phosphole chemistry of palladium(II) andplatinum(II) (80IC709 82IC2145 84IC449 85JA6939 89IC217). 

Palladium(II)-catalyzed cyclization of N-alkylation of allyl alcohols by ure-tanes and its application to the synthesis of natural saturated heterocycles 98YGK34. 

It was found [99JCS(PI )3713] that, in all cases, the formation of the deiodinated products 38 and 39 was accompanied by formation of the diynes 40 which were isolated in 60-90% yield. The authors believed that the mechanism of deiodination may be represented as an interaction ofbis(triphenylphosphine)phenylethynyl-palladium(II) hydride with the 4-iodopyrazole, giving rise to the bisftriphenylphos-phine)phenylethynyl palladium(II) iodide complex which, due to the reductive elimination of 1 -iodoalkyne and subsequent addition of alk-1 -yne, converts into the initial palladium complex. Furthermore, the interaction of 1-iodoalkynes with the initial alkyne in the presence of Cul and EtsN (the Cadiot-Chodkiewicz reaction) results in the formation of the observed disubstituted butadiynes 40 (Scheme 51). 

Diphenylimidazole with palladium acetate forms the cyclometallated complex 80 (X = OAc) (97AOC491). The acetate group is replaced by chloride or bromide when 80 (X = OAc) reacts with sodium chloride or lithium bromide, respectively, to give 80 (X = C1, Br). Bromide with diethyl sulfide forms the mononuclear complex 81. Similar reactions are known for 1 -acetyl-2-phenylimidazole (96JOM(522)97). 1,5-Bis(A -methylimidazol-2-yl)pen-tane with palladium(II) acetate gives the cyclometallated complex 82 (OOJOM (607)194). 

Dimethylbenzimidazolium iodide serves as a starting material for free carbenes (99CEJ1931, 99JA10626, 00AGE541) and carbene complexes (99JOM(585)241). Thus, with palladium(II) acetate it gives [L Pdl ] where L is... 

Biimidazole and bibenzimidazole with [(ri -2-RC3H )Pd(p-Cl)]2 (R = H, Me) taken in the 2 1 molar ratio in the presence of methanolic potassium hydroxide give complexes of the type 146 (83JCS(D)1729) and with [(ti -2-RC3H ) Pd(Mc2C0) ](C10 ) - 147. When the ratio of 2,2 -biimidazole or 2,2 -bibenz-imidazole and [(Ti -2-RC3H )Pd(p-Cl)]2 (R = H, Me) is 1 1, the homo-tetranuclear species 148 result. Heterotetranuclear palladium(II)-rhodium(I) complexes 149 (L2 = cod) follow from [(TiLcod)Rh(Hbim)] and [(ri -2-R-C3H )Pd(acac)]. They are readily carbonylated with complete substitution of... 

Dimethyl-1,2,4-triazolium iodide with palladium acetate yields the carbene adduct 182 (97JOM(530)259). Under water it undergoes cis-trans isomerization to 183. Some other derivatives were reported in 1981 (81BCSJ800). 1,1 -Methylenebis(4-alkyl-l,2,4-triazolium)diiodides (alkyl = /-Pr, n-Bu, octyl) with palladium(II) acetate give the mononuclear complexes [L Pdl ] (99EJIC1965), where L2= l,l -methylenebis(4-R-l,2,4-triazol-2-ylidene) (R = /-Pr, n-Bu, octyl). Thermolysis of the products in THF gives the rran -dinuclear complexes 184... 

R = /-Pr, n-Bu, octyl). The reaction of l,r-methylenebis(4-methyl-l,2, 4-tria2olium)diiodide with palladium(II) acetate however proceeds differently and gives the cationic dicarbene [L2Pd(02CMe)]I. 

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