Synthetic Route of 15746-57-3. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)
Redox transformations of bis(2,2?-bipyridine)(1-methyl-1-pyridin-2- yl-ethylamine)ruthenium(II)
The amineruthenium(II) complex Ru(bpy)2(mpea)2+ has been prepared by the direct reaction of 1-methyl-1-pyridin-2-yl-ethylamine (mpea) with Ru(bpy)2Cl2 in ethanol/water and isolated as the hexafluorophosphate salt. Electrochemical analysis of this complex shows that it undergoes sequential one-electron oxidations to an amidoruthenium(III) intermediate (E? = 1.086 V vs NHE) and then to an amidoruthenium(IV) (E? = 0.928 V) or imidoruthenium(IV) (E? = 1.083 V) complex, depending upon the solution pH (pKa = 2.62 for the amidoruthenium(IV) species). At higher potentials (Epa = 1.5 V in 1.0 M H2SO4), the amido- or imidoruthenium(IV) species is irreversibly oxidized to the corresponding nitrosoruthenium(II) complex. The mechanism for this transformation appears, on the basis of b3lyp/cpcm/cep-31g(d) computations, to proceed through an imidoruthenium(V) intermediate, which is rapidly attacked by water to yield a Ru(II)-bound hydroxylamine radical, which is readily oxidized and deprotonated to produce the nitrosoruthenium(II) complex. The nitrosoruthenium(II) complex is quantitatively reduced to the original [Ru(bpy)2(mpea)]2+ complex at relatively negative potentials (Epc = -0.2 V in 1.0 M H2SO4).
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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI