Reductive transformation of organic and inorganic nitrogen oxides on transition metal centers has been attracting much attention in relation to the mechanism of metalloenzymes involved in the nitrogen cycle in nature. We have recently demonstrated that the nitrosyl complexes [Cp~*Ru(NO)-(ar-py)](OTf) (Cp~* = η~5-C5(CH3)5; ar-py = C6H3(R)C5H4N-κ~2N,C-R = H, CH3; OTf = OSO,CF3) bearing an LX-type C-N chelate ligand undergo nucleophilic methylation to the nitrosyl ligand and subsequent protonation to afford the nitrosomethane-κN and N-methylhydroxylamido (CH3NHO-κ~2N,o) complexes.
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