Substitution-inert cobalt(II1) complexes containing an N-glycoside formed from ethylenediamine (en) and an aldose (o-mannose, L-rhamnose, or D-ribose) were synthesized by the oxidation of cobalt(l1) to cobalt(II1) in the presence of the diamine. It was found that [(en)2Co(02)(OH)Co(en)2]3+ is a reactive species toward aldoses in the reaction. The major product for each starting aldose was purified by column chromatography to yield red crystals. The isolated complexes were characterized by elemental analysis, conductivity measurements, and IH and I3C NMR, electronic absorption, and circular dichroism spectroscopies, the results of which show that the complexes are composed of a bidentate en and a tetradentate N-glycoside ligand. The structures of the sugar units were analyzed by means of the semiempirical AM1 calculations coupled with the conversion of the vicinal 'H-IH spin-spin coupling constants in the IH N M R spectra into torsion angles of the corresponding H-C-C-H fragments. The results of the calculations demonstrate that the D-mannose and L-rhamnose units take the pyranose form with the p-3S5 skew-boat conformation on the cobalt(II1) complexes, while the D-ribose unit adopts the furanose form with the w 2 E envelope conformation on the complex; in addition the sugar units of the N-glycoside ligands facially bind to the cobalt atom at three points through the donor atoms on CI, C2, and C3.
The interaction of sugars with various metal ions is well-known and is of current interest in bioinorganic chemistry in connection with metal-containing enzymes and industrial applications. Despite such a wide interest, very little is systematically known about the structural details of sugar-metal complexes.2-6In order to elucidate the interaction between sugars and transition metals, we have extensively studied the synthesis and characterization of substitution-labile nickel(I1) complexes containing N-glycoside(s) derived from the reaction of sugars and diamines.'-'' During a series of our investigations about Nglycoside systems formed from an aldose and a diamine with primary amino groups such as ethylenediamine or tri-methylenediami~~e,'-~ the structures of [ N i (~-G l c N -e n '~)~] Br,. 4 H 2 0 * and [N~(L-R~~-~~'~),]B~~.~H~O.CH~OH~ were determined ( I ) Present address: (aTakizawa, S.; Sugita, H.; Takahashi, T.; Tsubomura, T.; Shioi, H.; Yoshikawa, S. Curbohydr. Res. 1985, (8) Yano, S.; Sakai, Y.; Toriumi, K.; Ito, T.; Ito, H.; Yoshikawa, S. Inorg. Chem. 1985. 24, 498-504. (9) Shioi, H.; Yano, S.; Toriumi, K.; Ito, T.; Yoshikawa, S. J . Chem. SOC., Chem. Commun. 1983, 201-202.