STRUCTURAL CHEMISTRY OF METHYLPALLADIUM(II) AND ALLYLPALLADIUM(II) COMPLEXES CONTAINING CHIRAL THIOETHER AUXILIARIES

The molecular structures of three Pd-11 compounds are reported: a) the two [PdCl(Me)] complexes 7a and 8a each containing a different chiral N,S-chelate based on ([(dihydrooxazolyl)phenyl]methyl)-thioglucose ba ckbones, e.g., ([2-[(4S)-4,5-dihydro-4-isopiopyloxazol-2-yl-kappa N]ph enyl]methyl 2,3,4,6-tetra-O-acetyl-1-(thio-kappa S)-beta-D-glucopyrano side)methylpalladium (II) (7a) and b) one [Pd(eta(3)-C3H5)(PS)](+) cat ion in which the P,S-chelate stems from a phosphinofenocene and thioep hedrine-derived thioether donor, i.e., [(S)-1-(diphenylphosphino-kappa R,2S)-1-phenyl-2-(piperidin-1-yl)propyl]thio-kappa S}ethyl)ferrocene] (eta(3)-prop-2-enyl)palladium trifluoromethanesulfonate (11). In the methylpalladium compounds 7a and 8a the thioglucose-kappa S moiety is pseudo-axial (Figs. 2 and 3),whereas in the allyl complex, the thioeph edrine-kappa S moiety is markedly pseudo-equatorial (Fig. 5). It is su ggested, based on these results, that the shape (chiral pocket) of suc h coordinated chiral thioethers may not be readily predictable.