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

Quimica nova

Formiga, André Luiz Barboza¹  Nunes, Genebaldo S.²  Alexiou, Anamaria D. P.³  Araki, Koiti⁴  Toma, Henrique E.⁴ 

[1] Universidade Estadual de Campinas, Campinas, Brasil;Universidade Estadual do Sudoeste da Bahia, Itapetinga, Brasil;Universidade Presbiteriana Mackenzie, São Paulo, Brasil;Universidade de São Paulo, São Paulo, Brasil

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

DOI  :  10.1590/S0100-40422010001000008

学科分类：化学（综合）

来源: Sociedade Brasileira de Quimica

【 摘 要 】

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

【 授权许可】

CC BY