Understanding Electronic Ligand Perturbation over Successive Metal-Based Redox Potentials in Mononuclear Ruthenium-Aqua Complexes

作者：Vaquer Lydia; Miro Pere; Sala Xavier; Bozoglian Fernando; Masllorens Ester; Benet Buchholz Jordi; Fontrodona Xavier; Parella Teodor; Romero Isabel; Roglans Anna; Rodriguez Montserrat; Bo Carles^*; Llobet Antoni

来源：ChemPlusChem, 2013, 78(3): 235-243.

DOI：10.1002/cplu.201200268

• carbenes
• density functional calculations
• nitrogen heterocycles
• redox chemistry
• ruthenium

A family of new ruthenium complexes containing a combination of polypyridyl and carbene ligands has been prepared and characterized from structural, spectroscopic, and redox viewpoints both experimentally and computationally. Interestingly, a correlation between E1/2, defined as the difference between E1/2(RuIV/III) and E1/2(RuIII/II), and the activity and selectivity of some catalytic oxidation processes has been clearly established. A density functional theory study on the synthesized species has been carried out revealing a correlation between the number of carbene ligands and E1/2, and consequently with the RuIII disproportionation. The reactivity of these complexes has been tested with regard to the electrocatalytic oxidation of benzyl alcohol.

• 出版日期2013-3