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Abstract:

Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (where Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1,2,3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1,0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an {MNO} 6 species with an almost-linear RuNO arrangement at 178.1(3)°. The compound [(Por)Ru(NO)(H2O)]BF4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP•- and 1290 cm-1 for TPP•-), from the small shift of ∼20 cm-1 for νNO and from the EPR signal at g iso ≈ 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm-1 shift in νNO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm-1 shift in νNO. The EPR response of the NO• complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H 2O or pyridines, was calculated to be centered at the porphyrin π system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has about 50% π*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex. © 2008 American Chemical Society.

Registro:

Documento: Artículo
Título:Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies
Autor:Singh, P.; Das, A.K.; Sarkar, B.; Niemeyer, M.; Roncaroli, F.; Olabe, J.A.; Fiedler, J.; Záliš, S.; Kaim, W.
Filiación:Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany
Departamento de Química Inorgánica, Analítica Y Química Física, INQUIMAE, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic
Palabras clave:ligand; metalloporphyrin; nitric oxide; ruthenium; article; chemistry; electrochemistry; electron spin resonance; infrared spectrophotometry; oxidation reduction reaction; quantum theory; ultraviolet spectrophotometry; X ray crystallography; Crystallography, X-Ray; Electrochemistry; Electron Spin Resonance Spectroscopy; Ligands; Metalloporphyrins; Nitric Oxide; Oxidation-Reduction; Quantum Theory; Ruthenium; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet
Año:2008
Volumen:47
Número:16
Página de inicio:7106
Página de fin:7113
DOI: http://dx.doi.org/10.1021/ic702371t
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:nitric oxide, 10102-43-9; ruthenium, 7440-18-8; Ligands; Metalloporphyrins; Nitric Oxide, 10102-43-9; Ruthenium, 7440-18-8
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v47_n16_p7106_Singh

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Citas:

---------- APA ----------
Singh, P., Das, A.K., Sarkar, B., Niemeyer, M., Roncaroli, F., Olabe, J.A., Fiedler, J.,..., Kaim, W. (2008) . Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies. Inorganic Chemistry, 47(16), 7106-7113.
http://dx.doi.org/10.1021/ic702371t
---------- CHICAGO ----------
Singh, P., Das, A.K., Sarkar, B., Niemeyer, M., Roncaroli, F., Olabe, J.A., et al. "Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies" . Inorganic Chemistry 47, no. 16 (2008) : 7106-7113.
http://dx.doi.org/10.1021/ic702371t
---------- MLA ----------
Singh, P., Das, A.K., Sarkar, B., Niemeyer, M., Roncaroli, F., Olabe, J.A., et al. "Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies" . Inorganic Chemistry, vol. 47, no. 16, 2008, pp. 7106-7113.
http://dx.doi.org/10.1021/ic702371t
---------- VANCOUVER ----------
Singh, P., Das, A.K., Sarkar, B., Niemeyer, M., Roncaroli, F., Olabe, J.A., et al. Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: Structural, spectroelectrochemical (IR, UV-Visible, and EPR), and theoretical studies. Inorg. Chem. 2008;47(16):7106-7113.
http://dx.doi.org/10.1021/ic702371t