Strong metal-to-ligand -backbonding weakens the N-N bond strength in 2-pyridinealdazine coordinated to tetraammineruthenium(II)

CATTANEO, MAURICIO; ALBORÉS, PABLO; FAGALDE, FLORENCIA; KATZ, NÉSTOR E

INORGANIC CHEMISTRY COMMUNICATIONS

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2017 vol. 80 p. 69 - 71

1387-7003

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 Nsingle bondN 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.