Reference 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)
The compounds [(acac)2RuIII(mu-H2L 2-)RuIII(acac)2] (rac, 1, and meso, 1?) and [(bpy)2RuII(mu-H2L?-) RuII(bpy)2](ClO4)3 (meso, [2](ClO4)3) have been structurally, magnetically, spectroelectrochemically, and computationally characterized (acac- = acetylacetonate, bpy = 2,2?-bipyridine, and H4L = 1,4-diamino-9,10-anthraquinone). The N,O;N?,O?-coordinated mu-H2Ln- forms two beta-ketiminato-type chelate rings, and 1 or 1? are connected via NH···O hydrogen bridges in the crystals. 1 exhibits a complex magnetic behavior, while [2](ClO4)3 is a radical species with mixed ligand/metal-based spin. The combination of redox noninnocent bridge (H 2L0 ? ? ? ?H2L 4-) and {(acac)2RuII} ? ?{(acac) 2RuIV} or {(bpy)2RuII} ? {(bpy)2RuIII} in 1/1? or 2 generates alternatives regarding the oxidation state formulations for the accessible redox states (1n and 2n), which have been assessed by UV-vis-NIR, EPR, and DFT/TD-DFT calculations. The experimental and theoretical studies suggest variable mixing of the frontier orbitals of the metals and the bridge, leading to the following most appropriate oxidation state combinations: [(acac) 2RuIII(mu-H2L?-)Ru III(acac)2]+ (1+) ? [(acac)2RuIII(mu-H2L2-)Ru III(acac)2] (1) ? [(acac)2Ru III(mu-H2L?3-)RuIII(acac) 2]-/[(acac)2RuIII(mu-H 2L2-)RuII(acac)2]- (1-) ? [(acac)2RuIII(mu-H 2L4-)RuIII(acac)2] 2-/[(acac)2RuII(mu-H2L 2-)RuII(acac)2]2- (12-) and [(bpy)2RuIII(mu-H2L?-) RuII(bpy)2]4+ (24+) ? [(bpy)2RuII(mu-H2L?-)Ru II(bpy)2]3+/[(bpy)2Ru II(mu-H2L2-)RuIII(bpy) 2]3+ (23+) ? [(bpy)2Ru II(mu-H2L2-)RuII(bpy) 2]2+ (22+). The favoring of RuIII by sigma-donating acac- and of RuII by the pi-accepting bpy coligands shifts the conceivable valence alternatives accordingly. Similarly, the introduction of the NH donor function in H2L n as compared to O causes a cathodic shift of redox potentials with corresponding consequences for the valence structure.
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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI