Artículos de revistas
Nitric Oxide As An Activation Agent For Nucleophilic Attack In Trans-[ru(no)(nh3)4{p(oet)3}](pf 6)3
Registro en:
Journal Of The Brazilian Chemical Society. , v. 21, n. 7, p. 1266 - 1273, 2010.
1035053
2-s2.0-77954267952
Autor
Metzker G.
Toledo Jr. J.C.
Lima F.C.A.
Magalhaes A.
Cardoso D.R.
Franco D.W.
Institución
Resumen
The complex trans-[Ru(NO)(NH3)4{P(OEt) 3}](PF6)3 undergoes nucleophilic attack on the phosphorus ester ligand in the solid state yielding trans-[Ru(NO)(NH 3)4{P(OH)(OEt)2}](PF6)3. The reaction was monitored and the products analyzed using nuclear magnetic resonance spectroscopy (31P{1H} CP-MAS NMR and 31P{1H} NMR), infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR), cyclic voltammetry (CV), electronic spectroscopy (UV-Vis) and elemental analysis. According to experimental data and quantum mechanical calculations (DFT), the reaction proceeds in the solid state by the nucleophilic attack on the phosphorus ligand, promoted by the strong polarization along the PIII-RuII-NO+ axis induced by the nitrosyl ligand, and takes place following the Michaelis-Arbusov type mechanism for phosphorus ester hydrolysis. 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