The reactions of tridentate cationic palladium(II) complexes with olefins and nucleophiles

Heinz Bernhard Kraatz, David Milstein

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

The reaction of the chelating bisphosphine 1,3-bis(diphenylphosphino)xylene (dppxH) 1 with PdCl2(NCMe)2 gives (dppx)PdCl 3. Analogously, 1,3-bis(bis(p-dimethylaniline)phosphino)xylene (dappxH) 2 yields (dappx)PdCl 4. Halide abstraction with AgBF4 leads cleanly to the ionic complexes [(dppx)Pd-solv]+ (BF4)- 5 and [(dappx)Pd-solv]+ (BF4)- 6 (solv = solvent); in solution, there is no evidence for interaction between anion and cation. Norbornene adds to 5 and 6 to give the corresponding olefin complexes [(dppx)Pd(nor)]+ (BF4)- 7 [(dappx)Pd(nor)]+(BF4)- 8. The olefin is only weakly bound to the metal center and can be easily displaced by nucleophiles, as demonstrated by the reaction of 7 with HO-, MeO-, CH2 = CH(CH2)4)O- and NH2Ph, to give the corresponding Pd(II)-Nuc complexes, (dppx)PdOH 10, (dppx)PdOMe 11, (dppx)PdO(CH2)4CHCH2 12 and [(dppx)-PdNH2Ph]+(BF4)- 13. The crystal structure of [(dppx)PdNH2Ph]+(BF4)·1.5 CH2Cl2 13 has been determined by an X-ray diffraction study at 113 K. The angle P(1)PdP(2) is 160.8(3)°, indicating substantial steric congestion because of the size of the aniline ligand. In the solid state, cation and anion are associated via hydrogen bonding in a NH ...· F bridge.

Original languageEnglish
Pages (from-to)223-232
Number of pages10
JournalJournal of Organometallic Chemistry
Volume488
Issue number1-2
Publication statusPublished - Feb 22 1995

Fingerprint

Nucleophiles
nucleophiles
Palladium
Alkenes
Xylene
alkenes
Olefins
Anions
Cations
palladium
Negative ions
Positive ions
xylene
Xylenes
Hydrogen Bonding
Aniline
Chelation
X-Ray Diffraction
anions
cations

Keywords

  • Alkoxide
  • Biphosphine
  • Crystal structure
  • Nucleophile
  • Olefin complexes
  • Palladium

ASJC Scopus subject areas

  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

The reactions of tridentate cationic palladium(II) complexes with olefins and nucleophiles. / Kraatz, Heinz Bernhard; Milstein, David.

In: Journal of Organometallic Chemistry, Vol. 488, No. 1-2, 22.02.1995, p. 223-232.

Research output: Contribution to journalArticle

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abstract = "The reaction of the chelating bisphosphine 1,3-bis(diphenylphosphino)xylene (dppxH) 1 with PdCl2(NCMe)2 gives (dppx)PdCl 3. Analogously, 1,3-bis(bis(p-dimethylaniline)phosphino)xylene (dappxH) 2 yields (dappx)PdCl 4. Halide abstraction with AgBF4 leads cleanly to the ionic complexes [(dppx)Pd-solv]+ (BF4)- 5 and [(dappx)Pd-solv]+ (BF4)- 6 (solv = solvent); in solution, there is no evidence for interaction between anion and cation. Norbornene adds to 5 and 6 to give the corresponding olefin complexes [(dppx)Pd(nor)]+ (BF4)- 7 [(dappx)Pd(nor)]+(BF4)- 8. The olefin is only weakly bound to the metal center and can be easily displaced by nucleophiles, as demonstrated by the reaction of 7 with HO-, MeO-, CH2 = CH(CH2)4)O- and NH2Ph, to give the corresponding Pd(II)-Nuc complexes, (dppx)PdOH 10, (dppx)PdOMe 11, (dppx)PdO(CH2)4CHCH2 12 and [(dppx)-PdNH2Ph]+(BF4)- 13. The crystal structure of [(dppx)PdNH2Ph]+(BF4)·1.5 CH2Cl2 13 has been determined by an X-ray diffraction study at 113 K. The angle P(1)PdP(2) is 160.8(3)°, indicating substantial steric congestion because of the size of the aniline ligand. In the solid state, cation and anion are associated via hydrogen bonding in a NH ...· F bridge.",
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N2 - The reaction of the chelating bisphosphine 1,3-bis(diphenylphosphino)xylene (dppxH) 1 with PdCl2(NCMe)2 gives (dppx)PdCl 3. Analogously, 1,3-bis(bis(p-dimethylaniline)phosphino)xylene (dappxH) 2 yields (dappx)PdCl 4. Halide abstraction with AgBF4 leads cleanly to the ionic complexes [(dppx)Pd-solv]+ (BF4)- 5 and [(dappx)Pd-solv]+ (BF4)- 6 (solv = solvent); in solution, there is no evidence for interaction between anion and cation. Norbornene adds to 5 and 6 to give the corresponding olefin complexes [(dppx)Pd(nor)]+ (BF4)- 7 [(dappx)Pd(nor)]+(BF4)- 8. The olefin is only weakly bound to the metal center and can be easily displaced by nucleophiles, as demonstrated by the reaction of 7 with HO-, MeO-, CH2 = CH(CH2)4)O- and NH2Ph, to give the corresponding Pd(II)-Nuc complexes, (dppx)PdOH 10, (dppx)PdOMe 11, (dppx)PdO(CH2)4CHCH2 12 and [(dppx)-PdNH2Ph]+(BF4)- 13. The crystal structure of [(dppx)PdNH2Ph]+(BF4)·1.5 CH2Cl2 13 has been determined by an X-ray diffraction study at 113 K. The angle P(1)PdP(2) is 160.8(3)°, indicating substantial steric congestion because of the size of the aniline ligand. In the solid state, cation and anion are associated via hydrogen bonding in a NH ...· F bridge.

AB - The reaction of the chelating bisphosphine 1,3-bis(diphenylphosphino)xylene (dppxH) 1 with PdCl2(NCMe)2 gives (dppx)PdCl 3. Analogously, 1,3-bis(bis(p-dimethylaniline)phosphino)xylene (dappxH) 2 yields (dappx)PdCl 4. Halide abstraction with AgBF4 leads cleanly to the ionic complexes [(dppx)Pd-solv]+ (BF4)- 5 and [(dappx)Pd-solv]+ (BF4)- 6 (solv = solvent); in solution, there is no evidence for interaction between anion and cation. Norbornene adds to 5 and 6 to give the corresponding olefin complexes [(dppx)Pd(nor)]+ (BF4)- 7 [(dappx)Pd(nor)]+(BF4)- 8. The olefin is only weakly bound to the metal center and can be easily displaced by nucleophiles, as demonstrated by the reaction of 7 with HO-, MeO-, CH2 = CH(CH2)4)O- and NH2Ph, to give the corresponding Pd(II)-Nuc complexes, (dppx)PdOH 10, (dppx)PdOMe 11, (dppx)PdO(CH2)4CHCH2 12 and [(dppx)-PdNH2Ph]+(BF4)- 13. The crystal structure of [(dppx)PdNH2Ph]+(BF4)·1.5 CH2Cl2 13 has been determined by an X-ray diffraction study at 113 K. The angle P(1)PdP(2) is 160.8(3)°, indicating substantial steric congestion because of the size of the aniline ligand. In the solid state, cation and anion are associated via hydrogen bonding in a NH ...· F bridge.

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