Strong metal-to-ligand π-backbonding weakens the N[sbnd]N bond in 2-pyridinealdazine coordinated to tetraammine-ruthenium(II)
A new mononuclear Ru(II) complex of formula [Ru(NH3)4(2-PCA)](PF6)2, (1), with 2-PCA = 2-pyridinealdazine, has been synthesized and characterized by spectroscopic and electrochemical techniques. The complete structure of (1) was determined by X-ray diffraction. A strong π-backbonding effect dπ(Ru) →...
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| Autores principales: | , , , |
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| Formato: | JOUR |
| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_13877003_v80_n_p69_Cattaneo |
| Aporte de: |
| Sumario: | A new mononuclear Ru(II) complex of formula [Ru(NH3)4(2-PCA)](PF6)2, (1), with 2-PCA = 2-pyridinealdazine, has been synthesized and characterized by spectroscopic and electrochemical techniques. The complete structure of (1) was determined by X-ray diffraction. A strong π-backbonding effect dπ(Ru) → π *(2-PCA) is disclosed in (1) by the high value of the RuIII/RuII redox potential and the short Ru-N(imine) bond length, which leads to a weakened N[sbnd]N bond in coordinated 2-PCA compared to that of the free ligand and thus to an enhanced reactivity in acidic media. In effect, the product of the reaction of excess Ru with 2-PCA is not the dinuclear species bridged by 2-PCA, but the already known 2-iminopyridine complex of tetraammineruthenium(II). DFT and TD-DFT calculations of (1) were consistent with experimental results and allowed the complete assignment of its UV–Visible bands. © 2017 Elsevier B.V. |
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