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- W2029584505 abstract "Abstract The equilibration and catalytic efficiency of (π-allyl)Pd complexes of N,P-chelates (L), [Pd(L)(η3-PhCHCHCHPh)]X, depending on their counteranions X have been studied by NMR spectroscopy and X-ray crystallography [L: 1-[4(S)-tert-butyl-2-oxazolin-2-yl]-2(PS)-(diphenylphosphino)ferrocene 1; 1-[4(S)-tert-butyl-2-oxazolin-2-yl]-2(PR)-(diphenylphosphino)ferrocene 2. X: Cl− and PF 6 - ]. Among the possible isomeric (π-allyl)Pd complexes, only endo-syn-syn 1n and 2n and exo-syn-syn isomers 1x and 2x were observed and the endo-isomer was found to be the major one in both cases. The endo/exo ratio determined in CDCl3 at room temperature was dependent both on the counterions and more so on the N,P-chelates (Cl−: 1n/1x = 9.8/1; 2n/2x = 5.3/1 vs PF 6 - : 1n/1x = 8.7/1; 2n/2x = 4.6/1). The counteranions significantly affected the rate as well as the enantioselectivity in the palladium catalyzed allylic substitution reaction. In the case of Cl− counterion, the catalytic reaction proceeded much faster and also provided a higher enantioselectivity compared to the case of the PF 6 - counterion. We have also evaluated the relative thermodynamic stability of the palladium complexes depending on ligands 1 and 2 by an equilibration study and by X-ray crystal structure analysis for the corresponding (π-allyl)palladium complexes. The higher reactivity of the less stable palladium complex of 1 over the more stable palladium complex of 2 is explained by a steric strain-reactivity argument." @default.
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- W2029584505 date "2006-09-01" @default.
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- W2029584505 title "Studies on the structure and equilibration of (π-allyl)palladium complexes of phosphino(oxazolinyl)ferrocene ligands" @default.
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- W2029584505 doi "https://doi.org/10.1016/j.tetasy.2006.08.002" @default.
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