Structural and electrochemical analysis reveals sequential ligand substitution and photoelimination in oxidized ruthenium nitrosyl complexes, highlighting distinct reaction pathways.
A one-electron oxidation species of the title complex, [Ru(NO)Cl5]−({RuNO}5-type nitrosyl complex), converted into cis-[Ru(NO)Cl4(CH3CN)]−({RuNO}6-type nitrosyl complex) at low temperature (5 °C) in the dark. The product species could be isolated and characterized. An X-ray structure determination showed a remarkably short N–O bond distance of the Ru–NO moiety: l(N–O) = 0.998 Å, l(Ru–N) = 1.787(5) Å, ∠Ru–N–O = 175.1(6)°. Under room light at 25 °C, the complex underwent a facile nitrosyl photoelimination to give trans-[RuCl4(CH3CN)2]−, the structure of which was also established. During the course of the reactions, two other unidentified species were confirmed to exist by cyclic voltammetry.
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Ooyama et al. (1995) studied this question.
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