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Abstract:

The photodetachment of NO from [MII(CN5NO]2- with M = Fe, Ru, and Os, upon laser excitation at various wavelengths (355, 420, and 480 nm) was followed by various techniques. The three complexes showed a wavelength-dependent quantum yield of NO production Φ (NO), as measured with an NO-sensitive electrode, the highest values corresponding to the larger photon energies. For the same excitation wavelength the decrease of Φ (NO) at 20 °C in the order Fe > Ru ≫ Os, is explained by the increasing M-N bond strength and inertness of the heavier metals. Transient absorption data at 420 nm indicate the formation of the [MIII(CN)5H2O]2- species in less than ca. 1 μs for M = Fe and Ru. The enthalpy content of [FeIII(CN)5H2O]2- with respect to the parent [FeII(CN)5NO]2- state is (190 ± 20) kJ mol-1, as measured by laser-induced optoacoustic spectroscopy (LIOAS) upon excitation at 480 nm. The production of [FeIII(CN5H2O]2- is concomitant with an expansion of (8 ± 3) ml mol-1 consistent with an expansion of the water bound through hydrogen bonds to the CN ligands plus the difference between NO release into the bulk and water entrance into the first coordination sphere. The activated process, as indicated by the relatively strong temperature dependence of the Φ (NO) values and by the temperature dependence of the appearance of the [FeIII(CN)5H2O]2- species, as determined by LIOAS, is attributed to NO detachment in less than ca. 100 ns from the isonitrosyl (ON) ligand (MS1 state). © The Royal Society of Chemistry and Owner Societies 2005.

Registro:

Documento: Artículo
Título:The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals
Autor:Videla, M.; Braslavsky, S.E.; Olabe, J.A.
Filiación:Max-Planck-Inst. Bioanorgan. Chem., Postfach 101365, D-45413 Mülheim an der Ruhr, Germany
INQUIMAE, Departamento de Quimica Inorganica, Universidad de Buenos Aires, Pab. II, Buenos Aires C1428EHA, Argentina
Palabras clave:iron complex; nitric oxide; osmium derivative; ruthenium complex; water; absorption; article; chemical bond; complex formation; controlled study; electrode; enthalpy; fluorescence spectroscopy; hydrogen bond; infrared spectroscopy; laser induced optoacoustic spectroscopy; low temperature procedures; mathematical computing; measurement; photochemistry; photon; priority journal; quantum yield; spectral sensitivity; spectroscopy; temperature dependence; ultraviolet spectrophotometry; Cyanides; Lasers; Metals, Heavy; Nitric Oxide; Nitroso Compounds; Organometallic Compounds; Photochemistry; Quantum Theory; Spectrum Analysis; Mus
Año:2005
Volumen:4
Número:1
Página de inicio:75
Página de fin:82
DOI: http://dx.doi.org/10.1039/b408367a
Título revista:Photochemical and Photobiological Sciences
Título revista abreviado:Photochem. Photobiol. Sci.
ISSN:1474905X
CODEN:PPSHC
CAS:nitric oxide, 10102-43-9; water, 7732-18-5; Cyanides; Metals, Heavy; Nitric Oxide, 10102-43-9; Nitroso Compounds; Organometallic Compounds
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1474905X_v4_n1_p75_Videla

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Citas:

---------- APA ----------
Videla, M., Braslavsky, S.E. & Olabe, J.A. (2005) . The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals. Photochemical and Photobiological Sciences, 4(1), 75-82.
http://dx.doi.org/10.1039/b408367a
---------- CHICAGO ----------
Videla, M., Braslavsky, S.E., Olabe, J.A. "The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals" . Photochemical and Photobiological Sciences 4, no. 1 (2005) : 75-82.
http://dx.doi.org/10.1039/b408367a
---------- MLA ----------
Videla, M., Braslavsky, S.E., Olabe, J.A. "The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals" . Photochemical and Photobiological Sciences, vol. 4, no. 1, 2005, pp. 75-82.
http://dx.doi.org/10.1039/b408367a
---------- VANCOUVER ----------
Videla, M., Braslavsky, S.E., Olabe, J.A. The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals. Photochem. Photobiol. Sci. 2005;4(1):75-82.
http://dx.doi.org/10.1039/b408367a