X-ray diffraction, multidimensional NMR spectroscopy, and MM2* calculations on chiral allyl complexes of palladium(II)

The solid-state structure of [Pd(eta3-C10H15)(R-(+)-BINAP)](CF3SO3), 3a, and multidimensional H-1, C-13, and P-31 NMR spectroscopy and MM2* calculations for [Pd(eta3-C10H15)(S,S-CHIRAPHOS)](CF3SO3), 4, are presented. The various solid- and solution-state structural parameters are compared with literature analogues and differences discussed. Some of the structural distortions observed in both of these eta3 beta-pinene allyl complexes are suggested to arise from electronic effects associated with substituted allyl ligands. The calculations suggest that the chiral array of four phenyl substituents for BINAP is somewhat different from that for CHIRAPHOS, with the phenyl groups for the latter having markedly less "axial" and "equatorial" character. Results from catalytic allylation experiments support the idea of a difference in the chiral array. Crystallographic data for 3a are as follows: space group P6(1) (No.169), a = 11.787(2) angstrom, c = 59.63(1) angstrom, V = 7179(2) angstrom3, Z = 6.