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Updated: Oct 13, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Structural, Electronic and Thermochemical preference for multi-PCET reactivity of Ruthenium(II)-Amine and
Mauricio Cattaneo1, Giovanny A Parada2,3, Adam L Tenderholt4
1INQUINOA (CONICET-UNT), Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, (4000) San Miguel de Tucumán, Argentina.
Abstract:
The multiredox reactivity of bioinorganic cofactors is often coupled to proton transfers. Here we investigate the structural, thermochemical, and electronic structure of ruthenium-amino/amido complexes with multi- proton-coupled electron transfer reactivity. The bis(amino)ruthenium(II) and bis(amido)ruthenium(IV) complexes [RuII(bpy)(en*)2]2+ (Ru ) and [RuIV(bpy)(en*-H2)2]2+ (Ru ) interconvert reversibly with the transfer of 2e-/2H+ (bpy = 2,2'-bipyridine, en* = 2,3-diamino-2,3-dimethylbutane). X-ray structures allow correlations between the structural and electronic parameters, and the thermochemical data of the 2e-/2H+ multi-square grid scheme. Redox potentials, acidity constants and DFT calculations reveal potential intermediates implicated in 2e-/2H+ reactivity with organic reagents in non-protic solvents, which shows a strong inverted redox potential favouring 2e-/2H+ transfer. This is suggested to be an attractive system for potential one-step (concerted) transfer of 2e-and 2H+ due to the small changes of the pseudo-octahedral geometries and the absence of charge change, indicating a relatively small overall reorganization energy.
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