Artículo
Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv)
Foi, Maria Ana
; Di Salvo, Florencia
; Doctorovich, Fabio
; Huck Iriart, Cristián
; Ramallo Lopez, Jose Martin
; Dürr, Maximilian; Ivanović Burmazović, Ivana; Stirnat, Kathrin; Garbe, Simon; Klein, Axel
Fecha de publicación:
06/2018
Editorial:
Royal Society of Chemistry
Revista:
Dalton Transactions
ISSN:
1477-9226
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
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).
Palabras clave:
Nitrosamines
,
Iridium
,
Oxidation
,
Complex
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Articulos(INIFTA)
Articulos de INST.DE INV.FISICOQUIMICAS TEORICAS Y APLIC.
Articulos de INST.DE INV.FISICOQUIMICAS TEORICAS Y APLIC.
Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos(SEDE CENTRAL)
Articulos de SEDE CENTRAL
Articulos de SEDE CENTRAL
Citación
Foi, Maria Ana; Di Salvo, Florencia; Doctorovich, Fabio; Huck Iriart, Cristián; Ramallo Lopez, Jose Martin; et al.; Synthesis and structural characterisation of unprecedented primary: N -nitrosamines coordinated to iridium(iv); Royal Society of Chemistry; Dalton Transactions; 47; 33; 6-2018; 11445-11454
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