
TY  - JOUR
A1  - O'Conner, CJ 
A1  - Bailey, AAT 
T1  - Mutarotation of D(+)-glucose. III. Evidence for cooperative and competitive nucleophilic catalysis by molybdenum(VI) and tungsten(VI) anions
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1984
VL  - 37
IS  - 7
SP  - 1411
EP  - 1426
KW  - 
UR  - https://doi.org/10.1071/CH9841411 
N2  - 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. 
ER  -

