Platinum complexes phosphine halides

Palladium complexes exhibit even higher catalytic activity and produce branched acids preferentially.132 133 The selectivity, however, can be shifted to the formation of linear acids by increasing the phosphine concentration.134 Temperature, catalyst concentration, and solvent may also affect the isomer ratio.135 Marked increase in selectivity was achieved by the addition of Group IVB metal halides to palladium136 and platinum complexes.137 Linear acids may be prepared with selectivities up to 99% in this way. The formic acid-Pd(OAc)2-l,4-bis(diphe-nylphosphino)butane system has been found to exhibit similar regioselectivities.138 Significant enhancements of catalytic activity of palladium complexes in car-bomethoxylation by use of perfluoroalkanesulfonic acid resin cocatalysts was reported.139,140... 

In methanol, Cl and 7tH+ ions exhibit a retarding effect. The stabilities of nickel(o)-phosphine complexes have been assessed these seem to depend more on the size of the phosphine and electronic effects on bond strengths are of secondary importance. In the oxidative addition of aryl halides to nickel(o)-phosphine complexes the reaction appears to proceed via an initial slow dissociation step to give Ni(PR3)2 which then attacks the organic species. The mechanism of oxidative elimination of these nickel species thus contrasts with that for the platinum(o)-phosphines where the dissociation of the ligand is rapid and the rate-determining step is that involving the redox interaction. The oxidation of tetrahedral cobalt(i) complexes with carbon tetrachloride has been described ... 

The most important of the tertiary phosphine complexes of platinum(IV) are Pt(QR3)2X4, generally prepared by halogen oxidation [174] of cis- or trans-Pt(QR3)2X2 (Q = P, As, R = alkyl Q = Sb, R = Me), since direct reaction of the platinum(IV) halides with the ligands leads to reduction. Once made, the platinum(IV) compounds are stable to reduction ... 

These ligands all form 1 1 complexes with platinum(II) halides which are non-conductors, monomeric and, in the solid state, contain one coordinated and two free double bonds. Proton n.m.r. data indicate that all three double bonds are equivalent in solution due to a rapid equilibrium between bonded and non-bonded —CH=CH2 groups. The phosphine and arsine complexes PtBraL (L = tvpp, tvpa) react with two equivalents of bromine giving what are believed to be platinum(II) species containing one coordinated double bond and two —CHBr-CHaBr groups arising from the saturation by bromine of the two free double bonds. 

Chelating phosphines can be used to generate Ph2PCH2CH2CH2P(H)Ph, Cy2PCH2CH2CH2P(H)Ph P(H)Ph with platinum(II) halides in the presence complexes of type (149).1431,1432... 

Divalent and tetravalent Pt probably form as many complexes as any other metal. The platinum(II) complexes are numerous with IV. S, halogens, and C. The letranitritoplatinum complexes are soluble in basic solution. Tetranitntoplatinum(II) ion is formed when a solution of plat-inum(II) chloride is boiled, at about neutral pH, with an excess of NaNO f. The ammonium salt may explode when heated. Generally, platinum-metal nitrites should be destroyed in solution. They never should be heated in the dry form. Pladnum(II) complexes most often have a coordination number of 4. Many compounds have been prepared with olefins, cyanides, nitriles, halides, isonitnles, amines, phosphines, arsines, and nitro compounds. 

Acetyl ligands, in niobium complexes, C-H BDEs, 1, 298 Achiral phosphines, on polymer-supported peptides, 12, 698 Acid halides, indium compound reactions, 9, 683 Acidity, one-electron oxidized metal hydrides, 1, 294 Acid leaching, in organometallic stability studies, 12, 612 Acid-platinum rf-monoalkynes, interactions, 8, 641 Acrylate, polymerization with aluminum catalysts, 3, 280 Acrylic monomers, lanthanide-catalyzed polymerization,... 

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