Abstract
Neutral complexes MII(C5Me5)(Q2-)(NO+) with M=Ru or Os and the catecholates Q2- with 3,5-di-tert-Bu (dtbc) or 3,4,5,6-tetrachloro substituents (tcc) were identified with the oxidation and charge states indicated. Reversible electron transfer was analyzed spectroelectrochem. (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, resp. Redox potentials were found to depend strongly on the donor or acceptor substitution pattern at Qn.
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