Evaluating electrochemical accessibility of 4f n 5d 1 and 4f n+1 Ln( ii ) ions in (C 5 H 4 SiMe 3 ) 3 Ln and (C 5 Me 4 H) 3 Ln complexes
Evaluating electrochemical accessibility of 4f n 5d 1 and 4f n+1 Ln( ii ) ions in (C 5 H 4 SiMe 3 ) 3 Ln and (C 5 Me 4 H) 3 Ln complexes
复制标题
评估 (C 5 H 4 SiMe 3 ) 3 Ln 和 (C 5 Me 4 H) 3 Ln 配合物中 4f n 5d 1 和 4f n 1 Ln( ii ) 离子的电化学可达性
DOI：
10.1039/d1dt02427b
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发表时间：
2021
影响因子：
4
通讯作者：
Evans, William J.
中科院分区：
文献类型：
--
作者：
Trinh, Michael T.;Wedal, Justin C.;Evans, William J.
在四氢呋喃中，以[nBu4N][BPh4]为支持电解质，用电化学方法测定了一系列Cp‘3LN络合物(Cp’=C5H4SiMe3，Ln=La3+)的还原电位(与Fc+/Fc之比)。Ln=Eu，Yb，Sm和Tm(−1.07~−2.83V)的Ln(III)/Ln(II)还原电势分别符合4F7，4F14，4F6和4F13Ln(II)离子的稳定趋势。Ln=Pr，Nd，Gd，Tb，Dy，Ho，Er和Lu形成4fn5d1 Ln(II)离子(n=2-14)的还原电位在−2.95V到−3.14V的窄范围内，La和Ce分别在−3.36V和−3.43V处观察到阴极事件。Ln(II)化合物[K(2.2.2-密码子)][Cp‘3Ln](Ln=Pr，Sm，Eu)的还原电位与Cp’3LN的还原电位相当。对9个(C5Me4H)3LN配合物的还原电位也进行了研究，发现它们比Cp‘3LN化合物的还原电位负0.05~0.24V。
The reduction potentials (reported vs. Fc+/Fc) for a series of Cp′3Ln complexes (Cp′ = C5H4SiMe3, Ln = lanthanide) were determined via electrochemistry in THF with [nBu4N][BPh4] as the supporting electrolyte. The Ln(III)/Ln(II) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f7, 4f14, 4f6, and 4f13 Ln(II) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4fn5d1 Ln(II) ions (n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln(II) compounds [K(2.2.2-cryptand)][Cp′3Ln] (Ln = Pr, Sm, Eu) match those of the Cp′3Ln complexes. The reduction potentials of nine (C5Me4H)3Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′3Ln compounds.