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:
CreatorsEmailORCIDORCID Put Code
Foi, AnaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Di Salvo, FlorenciaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Doctorovich, FabioUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Huck-Iriart, CristianUNSPECIFIEDorcid.org/0000-0001-5734-2499UNSPECIFIED
Martin Ramallo-Lopez, JoseUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Duerr, MaximilianUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Ivanovic-Burmazovic, IvanaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Stirnat, KathrinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Garbe, SimonUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Klein, AxelUNSPECIFIEDorcid.org/0000-0003-0093-9619UNSPECIFIED
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: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
X-RAY-ABSORPTION; COMPLEXES; REACTIVITY; OXIDATION; XANES; IR; EFFICIENTMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/17308

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