The synthesis, spectral studies and electrochemistry of 1,10-(phenanthroline)-bis-{1-alkyl-2-(arylazo)imidazole}ruthenium(II) perchlorate. Single crystal X-ray structure of [Ru(phen)(HaaiMe)2](ClO4)2 [phen=1,10-phenanthroline, HaaiMe=1-methyl-2-(phenylazo)imidazole]

Add time:08/16/2019    Source:sciencedirect.com

The hetero-tris-chelates of the formulae [Ru(phen)(RaaiR′)2](ClO4)2 [phen=1,10-phenanthroline, RaaiR′=1-alkyl-2-(arylazo)imidazole, p-RC6H4NNC3H2NN-1-R′, where R=H (a), Me (b), Cl (c) and R′=Me (2), Et (3), CH2Ph (4)] have been isolated from the reaction of ctc-[RuCl2(RaaiR′)2] with AgNO3+phen or [Ag(phen)2](ClO4) in acetone at 40 °C in the dark followed by the addition of NaClO4(aq). The structure of [Ru(phen)(HaaiMe)2](ClO4)2 has been confirmed by X-ray diffraction study and suggested stereoretentive nucleophilic substitution. The structure and stereochemistry of the complexes have been supported by 1H NMR data. Electronic spectra exhibit a strong metal-to-ligand charge transfer (MLCT) band at 515–530 nm along with a weak transition at 700–710 nm. Cyclic voltammograms show a Ru(III)/Ru(II) couple at 1.3–1.4 V versus saturated calomel electrode (SCE) along with three successive ligand reductions. The plot of the difference in potential of the first oxidation and reduction versus energy of the main MLCT band (ν̄CT) is linear.

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