PALLADIUM-ALLYL COMPLEXES BASED ON 3,17-DIOXO-4-ANDROSTENE - THE SOLID-STATE STRUCTURE OF [PD(ETA(3)-C19H29O2)(R-BINAP)]PF6

Several pi-allyl compounds of the form [Pd(eta(3)-C19H29O2)(bidentate) ](anion), derived from 3,17-dioxo-4-androstene, have been prepared (bi dentate = R-Binap, 3a; S,S-Chiraphos, 3b; l-2,2'-diyl)bis(3,5-di-tert- butylphenylphosphine), MeO-Biphep, 3c; the P,S-chelate phenylphosphino )benzylthio)-beta-D-glucopyranose), 7, phenanthroline, 8, and neocupro in, 9). The solid-state structure of [Pd(eta(3)-C19H29O2)(R-Binap)]PF6 has been determined by X-ray diffraction methods. It is suggested tha t 3a (and presumably other relatively large allyl complexes) accommoda tes the two large ligands by both hinging the allyl plane away from th e Binap and rotating the allyl ligand. Selected aspects of tile soluti on dynamics for 3a, 3c, and 9 have been followed by NOESY methods. All yl C-13 NMR data are reported for the complexes.