X-RAY-DIFFRACTION, MULTIDIMENSIONAL NMR-SPECTROSCOPY, AND MM2 ASTERISK CALCULATIONS ON CHIRAL ALLYL COMPLEXES OF PALLADIUM(II)

The solid-state structure of [Pd(eta3-C10H15)(R-(+)-BINAP)](CF3SO3), 3 a, and multidimensional H-1, C-13, and P-31 NMR spectroscopy and MM2 calculations for [Pd(eta3-C10H15)(S,S-CHIRAPHOS)](CF3SO3), 4, are pres ented. 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 associ ated with substituted allyl ligands. The calculations suggest that the chiral array of four phenyl substituents for BINAP is somewhat differ ent from that for CHIRAPHOS, with the phenyl groups for the latter hav ing 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 g roup P6(1) (No.169), a = 11.787(2) angstrom, c = 59.63(1) angstrom, V = 7179(2) angstrom3, Z = 6.