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

The redox chemistry of the N-nitrosamine complexes [IrCl<sub>5</sub>(RN(H)NO)]<sup>2-</sup> (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 spectroelectrochemistr...

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Autores principales:	Foi, María Ana, Di Salvo, Florencia, Doctorovich, Fabio, Huck Iriart, Cristián, Ramallo López, José Martín, Dürr, Maximilian, Ivanović Burmazović, Ivana, Stirnat, Kathrin, Garbe, Simon, Klein, Axel
Formato:	Articulo Preprint
Lenguaje:	Inglés
Publicado:	2018
Materias:	Química Nitrosamines Iridium Oxidation Complex
Acceso en línea:	http://sedici.unlp.edu.ar/handle/10915/100580 https://ri.conicet.gov.ar/11336/89316 https://pubs.rsc.org/en/content/articlelanding/2018/DT/C8DT02549E#!divAbstract
Aporte de:	SEDICI (UNLP) de Universidad Nacional de La Plata

id	I19-R120-10915-100580
record_format	dspace
institution	Universidad Nacional de La Plata
institution_str	I-19
repository_str	R-120
collection	SEDICI (UNLP)
language	Inglés
topic	Química Nitrosamines Iridium Oxidation Complex
spellingShingle	Química Nitrosamines Iridium Oxidation Complex Foi, María Ana Di Salvo, Florencia Doctorovich, Fabio Huck Iriart, Cristián Ramallo López, José Martín Dürr, Maximilian Ivanović Burmazović, Ivana Stirnat, Kathrin Garbe, Simon Klein, Axel Synthesis and structural characterisation of unprecedented primary N -nitrosamines coordinated to iridium(IV)
topic_facet	Química Nitrosamines Iridium Oxidation Complex
description	The redox chemistry of the N-nitrosamine complexes [IrCl<sub>5</sub>(RN(H)NO)]<sup>2-</sup> (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 Ir<sup>IV</sup> species but also partial decomposition of the oxidised species [Ir<sup>IV</sup>Cl<sub>5</sub>(RN(H)NO)]- on this timescale (minutes). Detailed studies on chemically oxidised solutions of the parent Ir<sup>III</sup> complexes gave evidence for paramagnetic Ir<sup>IV</sup> from NMR spectra. Final products of the decomposition were the corresponding alcohols and presumably [Ir<sup>III</sup>Cl<sub>5</sub>(L)]<sup>2-</sup> (L = N<sub>2</sub>, solvent, amine) complexes. Similar decomposition reactions of acidic DMSO solutions of [IrCl<sub>5</sub>(RN(H)NO)]<sup>2-</sup>revealed that this combination produces the so-called "activated" DMSO (Me<sub>2</sub>S+-O- or Me<sub>2</sub>S+-OE, with "E" being an electrophile) which oxidises the parent Ir<sup>III</sup> complexes. Finally, with the very reactive purple Ir<sup>IV</sup> compound (PPh<sub>4</sub>)[IrCl<sub>5</sub>(BnN(H)NO)], the first primary N-nitrosamine coordinated to [Ir<sup>IV</sup>Cl<sub>5</sub>]- 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).
format	Articulo Preprint
author	Foi, María Ana Di Salvo, Florencia Doctorovich, Fabio Huck Iriart, Cristián Ramallo López, José Martín Dürr, Maximilian Ivanović Burmazović, Ivana Stirnat, Kathrin Garbe, Simon Klein, Axel
author_facet	Foi, María Ana Di Salvo, Florencia Doctorovich, Fabio Huck Iriart, Cristián Ramallo López, José Martín Dürr, Maximilian Ivanović Burmazović, Ivana Stirnat, Kathrin Garbe, Simon Klein, Axel
author_sort	Foi, María Ana
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)
publishDate	2018
url	http://sedici.unlp.edu.ar/handle/10915/100580 https://ri.conicet.gov.ar/11336/89316 https://pubs.rsc.org/en/content/articlelanding/2018/DT/C8DT02549E#!divAbstract
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Synthesis and structural characterisation of unprecedented primary N -nitrosamines coordinated to iridium(IV)

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