Synthesis and characterization of square-planar palladium(II), platinum(II) and rhodium(I) complexes with a chiral pyridylphosphine hybrid ligand

Stoccoro, Sergio; Chelucci, Giorgio; Zucca, Antonio; Cinellu, Maria Agostina; Minghetti, Giovanni; Manassero, Mario

doi:10.1039/dt9960001295

Cited by 19 publications

(4 citation statements)

References 29 publications

(2 reference statements)

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“…Apparently, there is an interaction between this proton and the metal, both in the solid state and in solution. This phenomenon has been observed before in a similar complex . At 80 °C, the ring inversion was fast on the NMR time scale.…”

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Nickel and Palladium Complexes of Pyridine−Phosphine Ligands as Ethene Oligomerization Catalysts

et al. 2009

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Pyridine-phosphine ligands 1-5 have been used to prepare neutral nickel dichloride complexes, neutral methylpalladium chloride complexes, and cationic methylpalladium complexes. The ligands consist of a diphenylphosphine and a pyridine moiety and differ in the backbone connecting those donor groups. Nickel complexes 9-13 are paramagnetic complexes, and they were characterized by elemental analysis, high-resolution mass spectrometry, and, for 10 and 12, single-crystal X-ray diffraction. Neutral palladium complexes 14-18 were fully characterized. Single-crystal X-ray diffraction was performed on complexes 15 and 16, and variable-temperature NMR demonstrated that 16 exhibits slow inversion of the metallacycle. Cationic palladium species 19-23 were obtained from the neutral complexes after chloride abstraction. Like its neutral precursor, 21 showed slow ring inversion. The nickel species were evaluated as ethene oligomerization catalysts after activation with MAO. All complexes were highly active, with TOFs between 24 × 10 3 and 85 × 10 3 (mol C 2 H 4 ) • (mol Ni • h) -1 . Butenes were the major product in all cases, forming 76 to 96 mol % of the product. Selectivities for 1-butene were between 10% and 40%. The cationic palladium species showed a very low productivity for ethene oligomerization, with TOFs e16 (mol C 2 H 4 ) • (mol Pd • h) -1 and 38 to 88 mol % butenes as the main product.

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confidence: 86%

“…In complex 15 , the shortest Pd···H distance is 3.39 Å. The structure of 16 can be compared with the PdCl 2 complex of a similar pyridine−phosphine ligand with a backbone consisting of three aliphatic carbons . In this structure, there also is a relatively short Pd···H distance of 2.72(3) Å.…”

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Nickel and Palladium Complexes of Pyridine−Phosphine Ligands as Ethene Oligomerization Catalysts

et al. 2009

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“…The formation of complexes by phosphine 100 (PYDIPHOS) was thoroughly studied by spectral methods (IR spectroscopy, 31 P, 1 H and 13 C NMR spectroscopy) and mass spectrometry. 133,134 Both rhodium (101) and palladium (102) metal complexes were described as chelates (the structure of the complex 102 was confirmed by X-ray diffraction analysis); however, the data obtained for the complex 101 do not rule out unambiguously an alternative highly symmetrical binuclear structure with bridging coordination of the P,N-bidentate ligands of the `head-to-tail' type. 134 The enantioselectivity observed in catalytic reactions involving PYDIPHOS (100) is moderate.…”

Section: Ligands With Sp 2 -Hybridised Electron-donating Nitrogen Atomsmentioning

confidence: 99%

“…133,134 Both rhodium (101) and palladium (102) metal complexes were described as chelates (the structure of the complex 102 was confirmed by X-ray diffraction analysis); however, the data obtained for the complex 101 do not rule out unambiguously an alternative highly symmetrical binuclear structure with bridging coordination of the P,N-bidentate ligands of the `head-to-tail' type. 134 The enantioselectivity observed in catalytic reactions involving PYDIPHOS (100) is moderate. For hydroformylation of styrene in the presence of the complex 101, the ee is 28%; ethoxycarbonylation in the presence of the complex 102 results in ee of 20%; in the model allylic alkylation {the [Pd(All)Cl] 2 .…”

Section: Ligands With Sp 2 -Hybridised Electron-donating Nitrogen Atomsmentioning

confidence: 99%

Chiral P,N-bidentate ligands in coordination chemistry and organic catalysis involving rhodium and palladium

Gavrilov¹,

Polosukhin²

2000

Russ. Chem. Rev.

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Published data on the synthesis of rhodium and palla-Published data on the synthesis of rhodium and palladium complexes with optically active P,N-bidentate ligands and dium complexes with optically active P,N-bidentate ligands and their applications in homogeneous asymmetric catalysis are their applications in homogeneous asymmetric catalysis are summarised and discussed. The effect of the nature of the P,N-summarised and discussed. The effect of the nature of the P,Nbidentate compounds on the structure of the metal complexes and bidentate compounds on the structure of the metal complexes and on enantioselectivity in catalysis is examined. Allylic substitution, on enantioselectivity in catalysis is examined. Allylic substitution, cross-coupling, hydroboration and hydrosilylation catalysed by cross-coupling, hydroboration and hydrosilylation catalysed by Rh or Pd complexes with optically active P,N-bidentate ligands Rh or Pd complexes with optically active P,N-bidentate ligands are considered. The prospects for the development of this field of are considered. The prospects for the development of this field of chemistry are demonstrated. The bibliography includes 186 refer-chemistry are demonstrated. The bibliography includes 186 references ences. .

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Synthesis of new acyclic aminophosphites and their chelate complexes with rhodium(i) and palladium(ii)

et al. 2000

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New acyclic aminophosphites (RO)2POCH2CH2NMe2 (PN) (R = Et. Pr'. or adamantyl) characterized by various steric requirements of the phosphorus center were synthesized. The reacnons of [he aminophosphites with Pd(COD)CI 2 (COD is 1.5-cyclooctadiene) and [Rh(CO)~C1]_~ afforded the stable chelate mononuclear complexes PdCI2(PN) and RhCICO(PN}. respectively. The structures of the resulting compounds were established by ~H, ~3C. and 31p NMR and IR spectroscopy, X-ray diffraction analysis, laser and plasma desorption mass spectrometry, X-ray photoelectron spectroscopy, and sedimentation analysis.

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Synthesis and characterization of square-planar palladium(II), platinum(II) and rhodium(I) complexes with a chiral pyridylphosphine hybrid ligand

Cited by 19 publications

References 29 publications

Nickel and Palladium Complexes of Pyridine−Phosphine Ligands as Ethene Oligomerization Catalysts

Nickel and Palladium Complexes of Pyridine−Phosphine Ligands as Ethene Oligomerization Catalysts

Chiral P,N-bidentate ligands in coordination chemistry and organic catalysis involving rhodium and palladium

Synthesis of new acyclic aminophosphites and their chelate complexes with rhodium(i) and palladium(ii)

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