[Unusual coordination behavior of D-fructose towards dimethyltin(IV)2+: metal-promoted deprotonation of alcoholic hydroxyl groups in aqueous solutions at low pH].
To study the effect of the conformation of sugar hydroxy groups on metal complexation processes, complex formation of eight saccharides (D-fructose, L-sorbose, L-arabinose, D-arabinose, D-glucose, D-sorbitol, 2-deoxy-D-glucose and D-saccharose) with dimethyltin(IV)2+ cations was investigated in aqueous solution by potentiometric equilibrium measurements, 13C NMR, polarimetric and Mössbauer spectroscopic methods. The experimental results proved that deprotonation of D-fructose and L-sorbose is caused by the coordination of dimethyltin(IV)2+ in the unusual low pH interval 4-6 in contrast to the other saccharides deprotonated in analogous way at pH > 8. Increasing the pH of the solution resulted in the formation of further complexes. Stability and composition of the species was determined by potentiometric studies. 13C NMR measurements led to the assignment of the sugar OH groups participating in the processes. Mössbauer investigations in the quick-frozen solutions permitted the determination of the stereochemistry of tin(IV) in the complexes.
Nagy
L
L
József Attila Tudományegyetem, Szervetlen és Analitikai Kémia Tanszék, Szeged.
Buzás
N
N
Barátné
J H
JH
Gajda
T
T
Kuzmann
E
E
Vértes
A
A
Burger
K
K
D000438:Alcohols / Q000737:chemistry*; D002236:Carbohydrate Conformation; D005632:Fructose / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009005:Monosaccharides / Q000737:chemistry*; D009947:Organotin Compounds / Q000737:chemistry*; D011199:Potentiometry; D012996:Solutions; D013329:Structure-Activity Relationship
D000438:Alcohols; D009005:Monosaccharides; D009947:Organotin Compounds; D012996:Solutions; C039760:dimethyltin; D005632:Fructose