TY - JOUR
T1 - The reactions of tridentate cationic palladium(II) complexes with olefins and nucleophiles
AU - Kraatz, Heinz Bernhard
AU - Milstein, David
N1 - Funding Information:
This research was supported under Grant No. TA-MOU-CA 13041, Program in Science and Technology Cooperation, U.S. Agency for Internal Development. We thank the MINERVA Foundation, Munich, F.R. Germany for a post-doctoral fellowship to H.-B.K.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
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
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U2 - 10.1016/0022-328X(94)00027-A
DO - 10.1016/0022-328X(94)00027-A
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 -