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 language | English |
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Pages (from-to) | 223-232 |
Number of pages | 10 |
Journal | Journal of Organometallic Chemistry |
Volume | 488 |
Issue number | 1-2 |
Publication status | Published - Feb 22 1995 |
Keywords
- Alkoxide
- Biphosphine
- Crystal structure
- Nucleophile
- Olefin complexes
- Palladium
ASJC Scopus subject areas
- Materials Chemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Biochemistry