Several pi-allyl compounds of the form [Pd(eta(3)-C19H29O2)(bidentate)](anion), derived from 3,17-dioxo-4-androstene, have been prepared (bidentate = R-Binap, 3a; S,S-Chiraphos, 3b; (6'6-dimethoxybiphenyl-2,2'-diyl)bis(3,5-di-tert-butylphenylphosphine), MeO-Biphep, 3c; the P,S-chelate (2,3,4,6-tetra-O-acetyl-1-(2-diphenylphosphino)benzylthio)-beta-D-glucopyranose), 7, phenanthroline, 8, and neocuproin, 9). The solid-state structure of [Pd(eta(3)-C19H29O2)(R-Binap)]PF6 has been determined by X-ray diffraction methods. It is suggested that 3a (and presumably other relatively large allyl complexes) accommodates the two large ligands by both hinging the allyl plane away from the Binap and rotating the allyl ligand. Selected aspects of the solution dynamics for 3a, 3c, and 9 have been followed by NOESY methods. Allyl C-13 NMR data are reported for the complexes.
Palladium-allyl complexes based on 3,17-dioxo-4-androstene. The solid-state structure of [Pd(eta(3)-C19H29O2)(R-Binap)]PF6
DROMMI, DarioMembro del Collaboration Group
;
1997-01-01
Abstract
Several pi-allyl compounds of the form [Pd(eta(3)-C19H29O2)(bidentate)](anion), derived from 3,17-dioxo-4-androstene, have been prepared (bidentate = R-Binap, 3a; S,S-Chiraphos, 3b; (6'6-dimethoxybiphenyl-2,2'-diyl)bis(3,5-di-tert-butylphenylphosphine), MeO-Biphep, 3c; the P,S-chelate (2,3,4,6-tetra-O-acetyl-1-(2-diphenylphosphino)benzylthio)-beta-D-glucopyranose), 7, phenanthroline, 8, and neocuproin, 9). The solid-state structure of [Pd(eta(3)-C19H29O2)(R-Binap)]PF6 has been determined by X-ray diffraction methods. It is suggested that 3a (and presumably other relatively large allyl complexes) accommodates the two large ligands by both hinging the allyl plane away from the Binap and rotating the allyl ligand. Selected aspects of the solution dynamics for 3a, 3c, and 9 have been followed by NOESY methods. Allyl C-13 NMR data are reported for the complexes.Pubblicazioni consigliate
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