TY - JOUR
T1 - Reaction mechanism of diphenylborinic acid with d-fructose in aqueous solution
AU - Sobue, Yukika
AU - Sugaya, Tomoaki
AU - Iwatsuki, Satoshi
AU - Inamo, Msahiko
AU - Takagi, Hideo D.
AU - Odani, Akira
AU - Ishihara, Koji
N1 - Funding Information:
We wish to express our thanks for financial support from JSPS KAKENHI Grant Number 25410150 , and Waseda University Grants for Special Research Projects (Grant 2009B-123 and 2014K-6156 ).
PY - 2016/5/1
Y1 - 2016/5/1
N2 - The reaction of d-fructose with diphenylborinic acid (Ph2B(OH)), to which d-fructose cannot coordinate tridentately, was kinetically investigated in order to solve the reaction mechanism, and to find a clue to resolve the two-step reaction mechanism of boronic acid (RB(OH)2) with d-fructose. The title reaction was a single-step reaction under the pseudo first-order conditions with large excess d-fructose over Ph2B(OH), which suggests that the reaction of RB(OH)2 with d-fructose consists of the fast formation of a two-coordinate complex followed by the slow formation of a three-coordinate complex. The kinetic reactivity of Ph2B(OH) was considerably higher than that of its conjugate base, diphenylborinate ion (Ph2B(OH)2-). It was shown that Ph2B(OH)2- interacted with CHES buffer to form an outer-sphere complex, whereas no interaction was observed between Ph2B(OH) and CHES buffer. Both the free borinate ion and the restrained borinate ion into the outer-sphere complex react with d-fructose to form the chelate complex via stable binary and ternary outer-sphere complexes, respectively.
AB - The reaction of d-fructose with diphenylborinic acid (Ph2B(OH)), to which d-fructose cannot coordinate tridentately, was kinetically investigated in order to solve the reaction mechanism, and to find a clue to resolve the two-step reaction mechanism of boronic acid (RB(OH)2) with d-fructose. The title reaction was a single-step reaction under the pseudo first-order conditions with large excess d-fructose over Ph2B(OH), which suggests that the reaction of RB(OH)2 with d-fructose consists of the fast formation of a two-coordinate complex followed by the slow formation of a three-coordinate complex. The kinetic reactivity of Ph2B(OH) was considerably higher than that of its conjugate base, diphenylborinate ion (Ph2B(OH)2-). It was shown that Ph2B(OH)2- interacted with CHES buffer to form an outer-sphere complex, whereas no interaction was observed between Ph2B(OH) and CHES buffer. Both the free borinate ion and the restrained borinate ion into the outer-sphere complex react with d-fructose to form the chelate complex via stable binary and ternary outer-sphere complexes, respectively.
KW - Borinic acid
KW - Reaction mechanism
KW - d-Fructose
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U2 - 10.1016/j.molliq.2015.07.062
DO - 10.1016/j.molliq.2015.07.062
M3 - Article
AN - SCOPUS:84938718681
VL - 217
SP - 29
EP - 34
JO - Journal of Molecular Liquids
JF - Journal of Molecular Liquids
SN - 0167-7322
ER -