Artículo

Foi, A.; Salvo, F.D.; Doctorovich, F.; Huck-Iriart, C.; Ramallo-López, J.M.; Dürr, M.; Ivanović-Burmazović, I.; Stirnat, K.; Garbe, S.; Klein, A. "Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)" (2018) Dalton Transactions. 47(33):11445-11454
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Abstract:

The redox chemistry of the N-nitrosamine complexes [IrCl5(RN(H)NO)]2- (R = benzyl or n-butyl) was studied in detail. One-electron oxidations at around 200 mV vs. ferrocene/ferrocenium were reversible in cyclic voltammograms. UV-vis spectroelectrochemistry reveals spectra characteristic of IrIV species but also partial decomposition of the oxidised species [IrIVCl5(RN(H)NO)]- on this timescale (minutes). Detailed studies on chemically oxidised solutions of the parent IrIII complexes gave evidence for paramagnetic IrIV from NMR spectra. Final products of the decomposition were the corresponding alcohols and presumably [IrIIICl5(L)]2- (L = N2, solvent, amine) complexes. Similar decomposition reactions of acidic DMSO solutions of [IrCl5(RN(H)NO)]2-revealed that this combination produces the so-called "activated" DMSO (Me2S+-O- or Me2S+-OE, with "E" being an electrophile) which oxidises the parent IrIII complexes. Finally, with the very reactive purple IrIV compound (PPh4)[IrCl5(BnN(H)NO)], the first primary N-nitrosamine coordinated to [IrIVCl5]- was isolated and characterised by UV-vis absorption, FTIR, NMR spectroscopy, ultra-high resolution electrospray mass spectrometry (UHR-ESI-MS) and iridium L3 X-ray absorption near-edge spectroscopy (XANES). © 2018 The Royal Society of Chemistry.

Registro:

Documento: Artículo
Título:Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
Autor:Foi, A.; Salvo, F.D.; Doctorovich, F.; Huck-Iriart, C.; Ramallo-López, J.M.; Dürr, M.; Ivanović-Burmazović, I.; Stirnat, K.; Garbe, S.; Klein, A.
Filiación:Departamento de Química Inorgánica, Analítica, y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, INQUIMAE-CONICET, Ciudad Universitaria Pabellón 2 Piso 3, Buenos Aires, C1428EHA, Argentina
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad Nacional de la Plata, CONICET, Casilla de Correo 16 Sucursal 4, La Plata, 1900, Argentina
Escuela de Ciencia y Tecnología, CONICET, Universidad Nacional de San Martín (UNSAM), Campus Miguelete, 25 de Mayo y Francia, San Martín Provincia de Buenos Aires, 1650, United States
Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 1, Erlangen, 91058, Germany
University of Cologne, Department of Chemistry, Institute for Inorganic Chemistry, Greinstrasse 6, Cologne, D-50939, Germany
Palabras clave:Absorption spectroscopy; Coordination reactions; Fourier transform infrared spectroscopy; Iron compounds; Mass spectrometry; Nitrosamines; Nuclear magnetic resonance spectroscopy; Organometallics; Oxidation; Spectroelectrochemistry; Sulfonation; X ray absorption; Decomposition reaction; Electrospray mass spectrometry; One-electron oxidation; Partial decomposition; Spectra characteristic; Ultrahigh resolution; UV-Vis spectroelectrochemistry; X-ray absorption near edge spectroscopy; Iridium compounds
Año:2018
Volumen:47
Número:33
Página de inicio:11445
Página de fin:11454
DOI: http://dx.doi.org/10.1039/c8dt02549e
Título revista:Dalton Transactions
Título revista abreviado:Dalton Trans.
ISSN:14779226
CODEN:DTARA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v47_n33_p11445_Foi

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Citas:

---------- APA ----------
Foi, A., Salvo, F.D., Doctorovich, F., Huck-Iriart, C., Ramallo-López, J.M., Dürr, M., Ivanović-Burmazović, I.,..., Klein, A. (2018) . Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv). Dalton Transactions, 47(33), 11445-11454.
http://dx.doi.org/10.1039/c8dt02549e
---------- CHICAGO ----------
Foi, A., Salvo, F.D., Doctorovich, F., Huck-Iriart, C., Ramallo-López, J.M., Dürr, M., et al. "Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)" . Dalton Transactions 47, no. 33 (2018) : 11445-11454.
http://dx.doi.org/10.1039/c8dt02549e
---------- MLA ----------
Foi, A., Salvo, F.D., Doctorovich, F., Huck-Iriart, C., Ramallo-López, J.M., Dürr, M., et al. "Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)" . Dalton Transactions, vol. 47, no. 33, 2018, pp. 11445-11454.
http://dx.doi.org/10.1039/c8dt02549e
---------- VANCOUVER ----------
Foi, A., Salvo, F.D., Doctorovich, F., Huck-Iriart, C., Ramallo-López, J.M., Dürr, M., et al. Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv). Dalton Trans. 2018;47(33):11445-11454.
http://dx.doi.org/10.1039/c8dt02549e