Properties of Protic Ionic Liquids Comprised of N-Alkyldiethylenetriamine and Their Complexation of Copper(II) Ions
Properties of Protic Ionic Liquids Comprised of N-Alkyldiethylenetriamine and Their Complexation of Copper(II) Ions
复制标题
N-烷基二亚乙基三胺质子离子液体的性质及其与铜(II)离子的络合
DOI：
10.1002/ejic.201700568
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Iida Masayasu
中科院分区：
文献类型：
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作者：
Nakayama Chisayo;Harada Masafumi;Iida Masayasu
制备了由烷基多胺阳离子组成的质子离子液体（PIL），例如单质子化的N-己基二乙烯三胺（HHexdien+）和N-（2-乙基己基）二乙烯三胺（HEthexdien+），与双（三氟甲基磺酰基）酰胺（Tf2N-）和三氟乙酸盐（TFA-）偶联，并制备了它们的性质以及与铜（II）的相互作用使用差示扫描量热法(DSC)、可见吸收光谱以及 15 N NMR 和 13 C NMR 光谱研究离子。烷基二乙烯三胺（三胺）PIL 在比相应的烷基乙烯二胺（二胺）PIL 更低的温度下呈现液态，并且在所有研究的系统中它们都表现出玻璃化转变而没有结晶。烷基三胺的质子化主要发生在 N(1) 和 N(3) 胺部分，并取决于抗衡阴离子（Tf2N-或 TFA-）和烷基部分（己基或乙基己基）。测定了三胺 PIL 和二胺 PIL 的极性参数，例如 ET(30) (orETN)、π*、α 和 β，以检查胺效应。根据分离的铜(II)-烷基二亚乙基三胺络合物和分子溶剂中的Cu(ClO4)2的可见吸收光谱，推导出本螯合物-胺PIL中铜(II)离子的配位结构。 PIL 中形成的铜 (II)-三胺复合物的寿命估计约为 100 小时。使用 13C NMR 光谱顺磁弛豫时间在环境温度下为 10-2 秒。
Protic ionic liquids (PILs) comprised of alkylpolyaminium cations, such as monoprotonatedN‐hexyldiethylenetriaminium (HHexdien+) andN‐(2‐ethylhexyl)diethylenetriaminium (HEthexdien+), coupled with bis(trifluoromethylsulfonyl)amide (Tf2N–) and trifluoroacetate (TFA–) were prepared, and their properties and interactions with copper(II) ions were studied using differential scanning calorimetry (DSC), visible absorption spectra, and15N NMR and13C NMR spectroscopy. The alkyldiethylenetriaminium (triamine) PILs assume a liquid state at lower temperatures than the corresponding alkylethylenediaminium (diamine) PILs, and they exhibit a glass transition without crystallization for all of the systems studied. The protonation of the alkyltriamines predominantly occurs at the N(1) and N(3) amine moieties and depends on the counteranions (Tf2N–or TFA–) and the alkyl moiety (hexyl or ethylhexyl). The polarity parameters, such asET(30) (orETN), π*,α, andβ, were determined for the triamine PILs, as well as for the diamine PILs, to examine the amine effect. The coordination structure of the copper(II) ion in the present chelate–amine PILs was deduced based on the visible absorption spectra for the isolated copper(II)–alkyldiethylenetriamine complexes and for Cu(ClO4)2in molecular solvents. The lifetime of the copper(II)–triamine complex formed in the PIL was estimated to be ca. 10–2s at ambient temperature using the13C NMR spectroscopic paramagnetic relaxation times.