An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity
The pseudo-octahedral nitrosyl species trans-[Ru(DMAP) 4(NO)(OH)] 2+ [1 2+, DMAP = 4-(dimethylamino)pyridine] was prepared by the reaction between [Ru(DMAP) 5(H 2O)] 2+ and NaNO 2 under mild conditions (room temperature, pH = 6-8), and precipitated with NaBF 4 or NaPF 6. Single-crystal X-ray diffrac...
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todo:paper_14341948_v_n27_p4301_OsaCodesido2023-10-03T16:14:22Z An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity Osa Codesido, N. De Candia, A.G. Weyhermüller, T. Olabe, J.A. Slep, L.D. Cyclic voltammetry Density functional calculations Electronic structure Nitrogen oxides Nitrosyl complexes Ruthenium The pseudo-octahedral nitrosyl species trans-[Ru(DMAP) 4(NO)(OH)] 2+ [1 2+, DMAP = 4-(dimethylamino)pyridine] was prepared by the reaction between [Ru(DMAP) 5(H 2O)] 2+ and NaNO 2 under mild conditions (room temperature, pH = 6-8), and precipitated with NaBF 4 or NaPF 6. Single-crystal X-ray diffraction data of 1(BF 4) 2·2H 2O point to a {RuNO} 6 electronic configuration of the cation, although there is a significant deviation from the expected linear arrangement of the RuNO moiety (Ru-N-O angle: 169.3°). The remarkably low wavenumber of the NO stretching band (ν NO) of 1832 cm -1 in the solid state corresponds to an electron-rich ligand environment with strong backbonding interactions between d π metal orbitals and π* NO orbitals of the (formal) NO + (nitrosonium) ligand. Consistently, the complex acts as a poor electrophile: it is extremely unreactive toward OH - and toward the stronger nucleophile cysteine. Cyclic voltammetry (CV) experiments show three reduction processes in acetonitrile. The first one at -0.50 V [vs. Ag/AgCl, KCl(s)] is reversible on the CV time scale. Spectroelectrochemical experiments (IR and UV/Vis) suggest that the reduced complex has a {RuNO} 7 configuration. The ν NO wavenumber of 1603 cm -1 agrees with a reduction mostly centered at the nitrosyl ligand. This species appears to be inert toward substitution in the coordination sphere, and the original {RuNO} 6 ion can be quantitatively recovered upon oxidation. In contrast, further reduction of this species is completely irreversible, even on the CV timescale, which is probably due to the lability of the presumably formed nitroxyl (NO -) ligand. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14341948_v_n27_p4301_OsaCodesido |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Cyclic voltammetry Density functional calculations Electronic structure Nitrogen oxides Nitrosyl complexes Ruthenium |
| spellingShingle |
Cyclic voltammetry Density functional calculations Electronic structure Nitrogen oxides Nitrosyl complexes Ruthenium Osa Codesido, N. De Candia, A.G. Weyhermüller, T. Olabe, J.A. Slep, L.D. An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| topic_facet |
Cyclic voltammetry Density functional calculations Electronic structure Nitrogen oxides Nitrosyl complexes Ruthenium |
| description |
The pseudo-octahedral nitrosyl species trans-[Ru(DMAP) 4(NO)(OH)] 2+ [1 2+, DMAP = 4-(dimethylamino)pyridine] was prepared by the reaction between [Ru(DMAP) 5(H 2O)] 2+ and NaNO 2 under mild conditions (room temperature, pH = 6-8), and precipitated with NaBF 4 or NaPF 6. Single-crystal X-ray diffraction data of 1(BF 4) 2·2H 2O point to a {RuNO} 6 electronic configuration of the cation, although there is a significant deviation from the expected linear arrangement of the RuNO moiety (Ru-N-O angle: 169.3°). The remarkably low wavenumber of the NO stretching band (ν NO) of 1832 cm -1 in the solid state corresponds to an electron-rich ligand environment with strong backbonding interactions between d π metal orbitals and π* NO orbitals of the (formal) NO + (nitrosonium) ligand. Consistently, the complex acts as a poor electrophile: it is extremely unreactive toward OH - and toward the stronger nucleophile cysteine. Cyclic voltammetry (CV) experiments show three reduction processes in acetonitrile. The first one at -0.50 V [vs. Ag/AgCl, KCl(s)] is reversible on the CV time scale. Spectroelectrochemical experiments (IR and UV/Vis) suggest that the reduced complex has a {RuNO} 7 configuration. The ν NO wavenumber of 1603 cm -1 agrees with a reduction mostly centered at the nitrosyl ligand. This species appears to be inert toward substitution in the coordination sphere, and the original {RuNO} 6 ion can be quantitatively recovered upon oxidation. In contrast, further reduction of this species is completely irreversible, even on the CV timescale, which is probably due to the lability of the presumably formed nitroxyl (NO -) ligand. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
| format |
JOUR |
| author |
Osa Codesido, N. De Candia, A.G. Weyhermüller, T. Olabe, J.A. Slep, L.D. |
| author_facet |
Osa Codesido, N. De Candia, A.G. Weyhermüller, T. Olabe, J.A. Slep, L.D. |
| author_sort |
Osa Codesido, N. |
| title |
An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| title_short |
An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| title_full |
An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| title_fullStr |
An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| title_full_unstemmed |
An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity |
| title_sort |
electron-rich {runo} 6 complex: trans-[ru(dmap) 4(no)(oh)] 2+ - structure and reactivity |
| url |
http://hdl.handle.net/20.500.12110/paper_14341948_v_n27_p4301_OsaCodesido |
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