TITLE:
Theoretical and Electrochemical Characterization of δ-RuCl2(Nazpy)2: Application to Oxidation of D-Glucose
AUTHORS:
Wawohinlin Patrice Ouattara, Kafoumba Bamba, Nahossé Ziao, Kouakou Nobel N’guessan
KEYWORDS:
DFT Calculation, HOMO-LUMO Analysis, NBO, Electrochemistry, Ruthenium Complex, D-Glucose
JOURNAL NAME:
American Journal of Analytical Chemistry,
Vol.7 No.1,
January
22,
2016
ABSTRACT: The heterogenized δ-RuCl2(Nazpy)2 deposited on carbon toray (CT) was studied
for the first time as electrochemical catalyst. Before, it was characterized by
visible-ultraviolet spectra and theoretically by TDDFT method at B3LYP/Lanl2DZ level.
It displayed an MLCT t2geg → π* transition where t2geg due to the structure of Nazpy
that considerably reduces energy between d AOs of Ru represents the HOMO of the
complex and π* is identified as the LUMO. Electrochemistry study shows
two redox ranges in both negative and positive sides of the potential. The positive
side that corresponds to the couple RuIV/RuIII of catalyst
appears to be active for oxidation of D-glucose in carbonate buffer with a high
turnover. Therefore, Keto-2-gluconic and gluconic acids were the two main products
obtained with respectively 80% and 17.6% of selectivity. Moreover, a
small amount of tartaric and glycol acids coming from the c-c bond cleavage
due to non-protection of the anomeric carbon of D-glucose were also observed.