Abstract
The reaction of the chelating bisphosphine 1,3-bis(diphenylphosphino)xylene (dppxH) 1 with PdCl 2(NCMe) 2 gives (dppx)PdCl 3. Analogously, 1,3-bis(bis( p-dimethylaniline)phosphino)xylene (dappxH) 2 yields (dappx)PdCl 4. Halide abstraction with AgBF 4 leads cleanly to the ionic complexes [(dppx)Pd-solv] + (BF 4) − 5 and [(dappx)Pd-solv] + (BF 4) − 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)] + (BF 4) − 7 [(dappx)Pd(nor)] +(BF 4) − 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 −, CH 2 = CH(CH 2) 4)O − and NH 2Ph, to give the corresponding Pd(II)-Nuc complexes, (dppx)PdOH 10, (dppx)PdOMe 11, (dppx)PdO(CH 2) 4CHCH 2 12 and [(dppx)-PdNH 2Ph] +(BF 4) − 13. The crystal structure of [(dppx)PdNH 2Ph] +(BF 4)·1.5 CH 2Cl 2 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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