Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)

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 speci...

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Autores principales:	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.
Formato:	JOUR
Materias:	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
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_14779226_v47_n33_p11445_Foi
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_14779226_v47_n33_p11445_Foi
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spelling	todo:paper_14779226_v47_n33_p11445_Foi2023-10-03T16:19:21Z Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv) 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. 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 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14779226_v47_n33_p11445_Foi
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	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
spellingShingle	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 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)
topic_facet	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
description	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.
format	JOUR
author	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.
author_facet	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.
author_sort	Foi, A.
title	Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
title_short	Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
title_full	Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
title_fullStr	Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
title_full_unstemmed	Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
title_sort	synthesis and structural characterisation of unprecedented primary: n -nitrosamines coordinated to iridium(iv)
url	http://hdl.handle.net/20.500.12110/paper_14779226_v47_n33_p11445_Foi
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Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)

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