
%0 Journal Article
%A O'Conner, CJ 
%A Bailey, AAT 
%T Mutarotation of D(+)-glucose. III. Evidence for cooperative and competitive nucleophilic catalysis by molybdenum(VI) and tungsten(VI) anions
%J Australian Journal of Chemistry
%D 1984/07/01
%V 37
%N 7
%P 1411-1426
%K 
%R https://doi.org/10.1071/CH9841411
%U https://www.publish.csiro.au/paper/CH9841411 
%X The rate of mutarotation of &#945;-D(+)-glucose is subject to general base catalysis by a variety of oxo anions. The relative magnitudes of the second-order rate constants are  B4O72->W7O246->Mo7O246- > HCO3->WO42->MoO42- Catalysis by W7O246- and Mo7O246- is competitive but that by WO42- and MoO42- is cooperative. A mechanism for catalysis by the polymeric anions is proposed which involves ion-pair formation between the anion and the conjugate acid of glucose. Specifically oriented aquation sheaths about the charged ions cause them to act as enhanced nucleophiles in the rate-determining step to form the aldehyde intermediate. Activation parameters support this model. 
