667. Carboxylates of palladium, platinum, and rhodium, and their adducts

Stephenson, T. A.; Morehouse, Sheila M.; Powell, A. R.; Heffer, J. P.; Wilkinson, Geoffrey

doi:10.1039/jr9650003632

Cited by 449 publications

(232 citation statements)

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“…Infrared bands at 1595 and 1410 cm-' in [Rh-(OAc)(TPPO)], are assigned to the antisymmetric and symmetric stretching frequencies of the MeCOO-group, indicative of a bridging acetate group (14).…”

Section: Resultsmentioning

confidence: 99%

Rhodium(I) Complexes of 1,2,5-Triphenylphosphole Oxide

Holah¹,

Hughes²,

Hui³

1972

Can. J. Chem.

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Rhodium trichloride hydrate and rhodium carbonyl chloride react with 1,2,5-triphenylphosphole oxide (TPPO) to produce a rhodium(I) complex [RhCl(TPPO)]2, where the metal is bonded to the ligand through the π system. This complex reacts with FeCl3 to produce RhCl(TPPO).FeCl3 where the iron is bonded through the oxygen of the P=O group. Reactions of [RhCl(TPPO)]2 with other species including nitrogen, phosphorus, and sulfur bases and carbon monoxide are described.

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Section: Resultsmentioning

confidence: 99%

Rhodium(I) Complexes of 1,2,5-Triphenylphosphole Oxide

Holah¹,

Hughes²,

Hui³

1972

Can. J. Chem.

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“…Palladium(II) acetate, and 1,3-bis(diphenylphosphine)propane, 1,1,1,3,3,3-hexafluoroisopropanol (99%) and CDCl 3 were Aldrich products. The complexes [PdX 2 (dppp)] (X = Cl, AcO, TsO) were prepared as reported in literature [31,32]. Carbon monoxide and ethylene were supplied by SIAD Company (Ôresearch gradeÕ, purity >99.9%).…”

Section: Reagentsmentioning

confidence: 99%

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

Cavinato

Vavasori

Toniolo

et al. 2005

Inorganica Chimica Acta

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The title complex has been synthesized by first reacting dppp with Pd(AcO) 2 in acetone and then with NaHSO 4 in water. It has been characterized by IR, NMR and X-ray diffraction studies. The 31 P NMR spectrum in DMSO shows a singlet at 16.62 ppm indicating that the two P atoms are equivalent and that the sulfate anion is weakly coordinating. The X-ray structure shows that the Pd atom is surrounded in an almost regular square planar environment by the two P atoms and by two O atoms of the sulfate anion and that the neutral complex is accompanied by a water molecule of crystallization. The Pd-P distances (2.217(1) and 2.233(1)) and the P-Pd-P angle (90.78(3)°) are close to those found in other complexes where the chelating diphosphine is the same. Also the Pd-O distances and the O-Pd-O bond angle are comparable to those of other relevant chelating ligands.In MeOH, the title complex, in combination with H 2 SO 4 , catalyses the CO-ethene copolymerization. The productivity reaches a maximum upon increasing the H 2 SO 4 /Pd ratio up to ca. 470 (7650 g of polyketone/g Pd h at 90°C and 45 atm, CO/ethene 1/1). The viscosity of the polyketone passes through a maximum of 0.95 dL/g in m-cresol when the above ratio is ca. 100. It has been proposed that acid promotes the copolymerization process by destabilizing the b-and c-chelates intermediates involved in chain growing process, thus favoring the insertion of the monomers. At relatively high acid concentration the lowering of productivity and viscosity suggests that the sulfate anion competes with the monomers for the coordination to the metal center.In H 2 O-CH 3 COOH as a solvent the productivity strongly depends on the H 2 O/CH 3 COOH ratio, as it passes through a maximum of 12 000 g polymer/g Pd h in the presence of ca. 60% of H 2 O. The productivity is significantly lower than that found when the acetate and chloride analogues are used (27 000 g polyketone/g Pd AE h). Thus, it is likely that the sulfate anion assists significantly the copolymerization process even though the concentration of CH 3 COOH/CH 3 COO À is much preponderant.

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“…(7). The acetic acid of high purity (Baker Chemical Co.) was dried by refluxing over triacetylborate, B(OAc),, and distilled (8).…”

Section: Mnterinlsmentioning

confidence: 99%

Interaction of Palladium(II) Acetate with Sodium and Lithium Acetate in Acetic Acid

Pandey¹,

Henry²

1974

Can. J. Chem.

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Palladium(I1) acetate in acetic acid in the absence of acetate ion exists as the trimeric species Pd,(OAc),. The reaction of the trimer with NaOAc o r LiOAc at 25" was not instantaneous. Spectral studies on fully equilibrated systems indicated the first equilibria involved transformation of trimer to dimer . This rate expression is consistent with substitution processes suggesting the slow step of the reaction is the S N 2 attack of solvent or acetate on a Pd(I1)-acetate bond to break one of the acetate bridges.In the NaOAc system conversion of trimer to dimer was complete at 0.2 M NaOAc. Further addition of NaOAc caused the dimer to be converted to monomer. L'acetate de palladium(I1) dans I'acide acetique, en l'absence d'ions acetate, existe sous la forme d'un trimere Pd3(OAc)6. La reaction du trimere avec NaOAc ou LiOAc a 25" n'ktait pas instantanee. Des etudes spectrales sur des systemes completement equilibrts indiquaient que le premier equilibre impliquait la transformation du trimere en dimere. Dans le cas du systeme NaOAc, la conversion du trirnere en dimere etait complete a 0.2 M NaOAc. Une nouvelle addition de NaOAc provoquait la conversion du dirnere en monomere.KZl tgale 7.6 x M-' a 25 "C. [Traduit par le journal]Can. J. Chem., 52, 1241 (1974)

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667. Carboxylates of palladium, platinum, and rhodium, and their adducts

Cited by 449 publications

References 0 publications

Rhodium(I) Complexes of 1,2,5-Triphenylphosphole Oxide

Rhodium(I) Complexes of 1,2,5-Triphenylphosphole Oxide

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

Interaction of Palladium(II) Acetate with Sodium and Lithium Acetate in Acetic Acid

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