Theoretical and Electrochemical Characterization of <i>δ</i>-RuCl<sub>2</sub>(Nazpy)<sub>2</sub>: Application to Oxidation of D-Glucose

Abstract

The heterogenized δ-RuCl 2 (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 t 2g e g → π* transition where t 2g e g 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 Ru IV /Ru III 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.

NBO Population Analysis and Electronic Calculation of Four Azopyridine Ruthenium Complexes by DFT Method

“…The regarding isomers are all admitted to be C 2 -symmetrical except δ-RuCl 2 (Nazpy) 2 that is C i -symmetrical. Anyhow, they all present a C 2 axis that makes both azopyridine ligands identical within each complex [8].…”