Universität zu Köln

Foi, Ana, Di Salvo, Florencia, Doctorovich, Fabio, Huck-Iriart, Cristian ORCID: 0000-0001-5734-2499, Martin Ramallo-Lopez, Jose, Duerr, Maximilian, Ivanovic-Burmazovic, Ivana, Stirnat, Kathrin, Garbe, Simon and Klein, Axel ORCID: 0000-0003-0093-9619 (2018). Synthesis and structural characterisation of unprecedented primary N-nitrosamines coordinated to iridium(IV). Dalton Trans., 47 (33). S. 11445 - 11455. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

The redox chemistry of the N-nitrosamine complexes [IrCl5(RN(H)N?O)](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 Ir-IV species but also partial decomposition of the oxidised species [(IrCl5)-Cl-IV(RN(H)N?O)](-) on this timescale (minutes). Detailed studies on chemically oxidised solutions of the parent Ir-III complexes gave evidence for paramagnetic Ir-IV from NMR spectra. Final products of the decomposition were the corresponding alcohols and presumably [(IrCl5)-Cl-III(L)](2-) (L = N-2, solvent, amine) complexes. Similar decomposition reactions of acidic DMSO solutions of [IrCl5(RN(H)N?O)](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 Ir-III complexes. Finally, with the very reactive purple Ir-IV compound (PPh4)[IrCl5(BnN(H)N?O)], the first primary N-nitrosamine coordinated to [(IrCl5)-Cl-IV](-) was isolated and characterised by UV-vis absorption, FTIR, NMR spectroscopy, ultra-high resolution electrospray mass spectrometry (UHR-ESI-MS) and iridium L-3 X-ray absorption near-edge spectroscopy (XANES).

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Foi, Ana UNSPECIFIED UNSPECIFIED UNSPECIFIED Di Salvo, Florencia UNSPECIFIED UNSPECIFIED UNSPECIFIED Doctorovich, Fabio UNSPECIFIED UNSPECIFIED UNSPECIFIED Huck-Iriart, Cristian UNSPECIFIED orcid.org/0000-0001-5734-2499 UNSPECIFIED Martin Ramallo-Lopez, Jose UNSPECIFIED UNSPECIFIED UNSPECIFIED Duerr, Maximilian UNSPECIFIED UNSPECIFIED UNSPECIFIED Ivanovic-Burmazovic, Ivana UNSPECIFIED UNSPECIFIED UNSPECIFIED Stirnat, Kathrin UNSPECIFIED UNSPECIFIED UNSPECIFIED Garbe, Simon UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-173087
DOI:	10.1039/c8dt02549e
Journal or Publication Title:	Dalton Trans.
Volume:	47
Number:	33
Page Range:	S. 11445 - 11455
Date:	2018
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language X-RAY-ABSORPTION; COMPLEXES; REACTIVITY; OXIDATION; XANES; IR; EFFICIENT Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/17308