Photolysis of a High-Spin Azidoiron(III) Complex Studied by Time-Resolved Fourier-Transform Infrared Spectroscopy.

Photolysis of a High-Spin Azidoiron(III) Complex Studied by Time-Resolved Fourier-Transform Infrared Spectroscopy.
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通过时间分辨傅里叶变换红外光谱研究高自旋叠氮铁 (III) 络合物的光解作用

DOI:
10.1002/chem.201700960
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发表时间:
2017
期刊:
影响因子:
--
通讯作者:
P. Vöhringer
P. Vöhringer
中科院分区:
--
文献类型:
--
作者:
J. Torres-Alacan;P. Vöhringer

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通过时间分辨傅里叶变换红外光谱研究了室温下液体乙腈溶液中高自旋叠氮铁(III)络合物[FeIII(Me3Cyclam-ac)(N3)]PF6([1]PF6)的激光闪光光解。 [1] 在 480 和 266 nm 处的激发诱导金属中心发生光还原并产生 [FeII(Me3Cyclam-ac)(NCCH3)]+([2]) 和叠氮基自由基。两种光产物都是通过清除实验独立检测到的。含金属片段用一氧化碳淬灭,生成铁(II)羰基络合物,而含氮片段用碘化物淬灭,形成叠氮化物阴离子。在 N3− 存在的情况下,光还原产生了难以捉摸的六氮自由基阴离子 N6.− 作为瞬态副产物。
The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal‐containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen‐containing fragment was quenched with iodide to form azide anions. In the presence of N3−, the photoreduction created the elusive hexanitrogen radical anion N6.−as a transient byproduct.
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