Abstract
AbstractNeutral complexes [MII(C5Me5)(Q2−)(NO+)] with M=Ru or Os and the catecholates Q2− with 3,5‐di‐tert‐butyl (dtbc) or 3,4,5,6‐tetrachloro substituents (tcc) were identified with the oxidation and charge states indicated. Reversible electron transfer was analyzed spectroelectrochemically (EPR, UV‐vis‐NIR, IR), supported by DFT calculations. Reversible reduction was observed for [Ru(C5Me5)(tcc)(NO)] to occur on the nitrosyl ligand to yield the NO radical complex [RuII(C5Me5)(tcc2−)(NO.)]−, whereas the stepwise oxidation yielded o‐semiquinone cations, [MII(C5Me5)(Q.−)(NO+)]+, and dications. The metals remained in the stable low‐spin d6 states, RuII and OsII, respectively. Redox potentials were found to depend strongly on the donor or acceptor substitution pattern at Qn.
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More From: Zeitschrift für anorganische und allgemeine Chemie
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