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Synthesis and structural characterisation of unprecedented primary N-nitrosamines coordinated to iridium(iv)†
Dalton Transactions ( IF 4 ) Pub Date : 2018-07-25 00:00:00 , DOI: 10.1039/c8dt02549e
Ana Foi 1, 2, 3, 4, 5 , Florencia Di Salvo 1, 2, 3, 4, 5 , Fabio Doctorovich 1, 2, 3, 4, 5 , Cristián Huck-Iriart 6, 7, 8, 9, 10 , José Martín Ramallo-López 6, 7, 8, 9, 10 , Maximilian Dürr 11, 12, 13, 14 , Ivana Ivanović-Burmazović 11, 12, 13, 14 , Kathrin Stirnat 14, 15, 16, 17, 18 , Simon Garbe 14, 15, 16, 17, 18 , Axel Klein 14, 15, 16, 17, 18
Affiliation  

The redox chemistry of the N-nitrosamine complexes [IrCl5(RN(H)N[double bond, length as m-dash]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 IrIV species but also partial decomposition of the oxidised species [IrIVCl5(RN(H)N[double bond, length as m-dash]O)]˙ 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)N[double bond, length as m-dash]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 IrIII complexes. Finally, with the very reactive purple IrIV compound (PPh4)[IrCl5(BnN(H)N[double bond, length as m-dash]O)], 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).

中文翻译:

合成和前所未有初级结构表征Ñ -nitrosamines协调,以铱(IV

详细研究了N-亚硝胺络合物[IrCl 5(RN(H)N [双键,长度为m-破折号]O)] 2–(R =苄基或丁基)的氧化还原化学。二茂铁/二茂铁相比,约200 mV的单电子氧化在循环伏安图中是可逆的。的UV-vis光谱电化学揭示的Ir的光谱特性IV氧化的物种的物种,而且部分分解物[Ir IV5(RN(H)N [双键,长度为m-破折号]O)]˙ -在此时间尺度(分钟)。对母体Ir III配合物的化学氧化溶液的详细研究为顺磁性Ir IV提供了证据从NMR光谱。分解的最终产物是相应的醇,大概是[Ir III Cl 5(L)] 2–(L = N 2,溶剂,胺)配合物。的酸性DMSO溶液类似的分解反应[的IrCl 5(RN(H)N [双键,长度为m-破折号]O)] 2-揭示该组合产生了所谓的“激活” DMSO(ME 2小号+ -O -或Me 2小号+ -OE ,其中“ E”为亲电子试剂)会氧化母体Ir III配合物。最后,用非常活泼的紫色Ir IV化合物(PPh 4)[IrCl5(BnN(H)N[双键,长度为m-破折号]O)]分离并与[Ir IV Cl 5 ] -配位的第一个伯N-亚硝胺,并通过紫外可见吸收,FTIR,NMR光谱,超高分辨率电喷雾质谱(UHR)进行表征-ESI-MS)和铱L 3 X射线吸收近边缘光谱(XANES)。
更新日期:2018-07-25
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