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 |
|---|---|
| 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 |
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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 journal › Article
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TY - JOUR
T1 - The reactions of tridentate cationic palladium(II) complexes with olefins and nucleophiles
AU - Kraatz, Heinz Bernhard
AU - Milstein, David
PY - 1995/2/22
Y1 - 1995/2/22
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.
KW - Alkoxide
KW - Biphosphine
KW - Crystal structure
KW - Nucleophile
KW - Olefin complexes
KW - Palladium
UR - http://www.scopus.com/inward/record.url?scp=0000261427&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000261427&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000261427
VL - 488
SP - 223
EP - 232
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -