The Electronic Character of the π-Allylic Group of π-Allylic Palladium Complexes

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Abstract
The substituent constants of the 2- and 1-positions of the π-allylic group of acetylacetonato (a) and cyclopentadienyl (b) derivatives of π-[2-(p-substituted phenyl)allyl]-(I) and π-(p-substituted cinnamyl)-palladium complexes(II) were estimated from their NMR spectra. The differences in the chemical shift (Δν, Hz) between the p-phenylene ring protons H1 and H2 of the complexes was found to be dependent upon the ligand and the substituent X. The plot of Δν against the substituent constant σp+, of X gave a fairly good linear relationship, and from the intercept of the straight line at Δν=0, the substituent constants of the 1-and 2-positions of the π-allylic group in the IIa or IIb complex and the Ia or Ib complex were estimated: σp: at the 1-position, 0.27 (IIa) or 0.24 (IIb), and at the 2-position, 0.21 (Ia) or 0.03 (Ib).

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