Redox and ligand-exchange chemistry of chromium(VI/V)-methyl glycoside system

摘要

In order to establish a general pattern for the redox and coordination chemistry of glycosides with Cr(VI) and Cr(V), reactions of a series of methyl glycosides with Cr(VI) and Cr(V) have been studied at different acidities. Oxidations of methyl alpha-and beta-D-glucopyranoside (GlclMe), methyl alpha- and beta-D-mannopyranoside (Man1Me), methyl alpha- and beta-D-galactopyranoside (GallMe) and methyl alpha- and beta-D-ribofuranoside (Rib1Me) by Cr(VI) proceed rapidly at pH <= 1, and yield Cr(III) and methyl glycofuranuronolactone as final products when an excess of methyl glycoside over Cu(VI) is used. At constant [H~+], the reaction follows the rate law -d[Cr(VI)]/dt = kappa_H [GlylMe] [Cr(VI)]. Relative reactivities of methyl glycosides toward Cr(VI) reduction are: beta-RiblMe > alpha-GallMe > alpha-RiblMe approx = beta-GallMe > beta-ManlMe > alpha-ManlM3 > alpha-GlclM3 > beta-GlclMe. This sequence is interpreted in terms of the degree of unfavorable steric interactions induced by the nonbonded 1,3-diaxial interactions in the respective GlylMe - Cr(VI) monochelate, which is formed in rapid equilibrium that precedes the rate determining step. For all the glycosides, the oxidation rate decreases with an increase in pH value and becomes negligible at pH > 5. At pH 5.5 and 7.5, addition of an excess of alpha-ManlMe or alpha(beta)-GallMe to an equimolar cysteine-Cr(VI) mixture, afforded two EPR triplets at g_(iso1) 1.9802 and g_(iso2) 1.9800/1 with A_(iso) 16.5(3) X 10~(-4) cm~(-1) in a 50:50 g_(iso1):g_(iso2) ratio. The EPR spectral parameters and the superhyperfine pattern of the signal are consistent with the presence of two geometric isomers of the [Cr~V O (cis-O~3, O~4-GallMe)_2]~- and [Cr~VO(cis-O~2,O~3-Man1Me)_2]~- complexes. The same final spectral pattern is observed at pH 7.5 for the ligand-exchange reaction of Man1Me and Gal1Me with [Cr~VO(ehba)_2]~- (ehba = 2-ethyl-2-hydroxybutanoato(2-)). No EPR signal is observed when an excess of Xil1Me or Glc1Me is added to an equimolar cysteine-Cr(VI) mixture. In the ligand-exchange reactions of [Cr~VO(ehba)_2]~- at pH 7.5 with Xil1Me or Glc1Me, a very low intensity EPR singlet is observed at g_(iso) 1.9799. These results show that only glycosides with one cis-diolato group (such as Man1Me and Gal1Me) are effective for stabilizing Cr(V) at pH 5.5 and 7.5. The high redox reactivity of methyl glycosides with Cr(V) at high [H~+] is attributed to the formation of [Cr~VO(O,O-glycoside) (OH_2)_3]~+ species (g_(iso) 1.9716), which are not observed at pH 5.5-7.5, where only the five-coordinate bis-chelate oxochromate(V) species are observed.