Hydrazine nitrosation of a metal-bound nitric oxide: structural evidence for the formation of an ammine complex.
Hydrazine nitrosation of [Ru(NO)(py(si)S4)]Br.THF (1) (py(si)S4(2-) = 2,6-bis(3-triphenylsilyl-2-sulfanylphenylthiomethyl)pyridine2-) in methanol/DMF led to the formation of mononuclear ammine complex [Ru(NH3)(py(si)S4)] (2) and N2O, whereas the reaction performed in THF/CH2Cl2/toluene afforded thioether-bridged dinuclear ammine complex [(NH3)Ru(mu-py(si)S4)Ru(py(si)S4)] (3). Compound 2 dimerizes in solution at room temperature to form 3 and is regenerated upon treatment of 3 with NH3. A plausible mechanism for the hydrazine nitrosation of 1 has been proposed. The reaction of 1 with NH3 or N3- does not lead to a nucleophilic attack at the NO+ ligand but to a deprotonation that yields neutral nitrosyl complex [Ru(NO){py(si)S4(H+)}] (4), which is supported by density functional theory calculations.
Prakash
Raju
R
Institut für Anorganische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany. raju.prakash@chemie.uni-erlangen.de
Götz
Andreas W
AW
Heinemann
Frank W
FW
Görling
Andreas
A
Sellmann
Dieter
D
D000588:Amines / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006834:Hydrazines / Q000737:chemistry*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry*; D009603:Nitroso Compounds / Q000138:chemical synthesis*; D013055:Spectrophotometry, Infrared
D000588:Amines; D006834:Hydrazines; D007202:Indicators and Reagents; D008670:Metals; D009603:Nitroso Compounds; D009569:Nitric Oxide