Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

Química Nova

Henrique E. Toma²  Koiti Araki²  André Luiz Barboza Formiga¹  Anamaria D. P. Alexiou¹  Genebaldo S. Nunes¹ 

[1] ,Universidade de São Paulo Instituto de Química São Paulo SP ,Brasil

关键词: ruthenium-acetate clusters;    methanol oxidation;    electrocatalysis;   

DOI  :  10.1590/S0100-40422010001000008

来源: SciELO

【 摘 要 】

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

【 授权许可】

CC BY-NC   
 All the contents of this journal, except where otherwise noted, is licensed under a Creative Commons Attribution License