Synthesis and electronic properties of a pentafluoroethyl-derivatized nickel pincer complex.
Synthesis and electronic properties of a pentafluoroethyl-derivatized nickel pincer complex.
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五氟乙基衍生的镍钳配合物的合成和电子性质。
DOI：
10.1039/c2dt30131h
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发表时间：
2012
影响因子：
4
通讯作者：
David A. Vicic
中科院分区：
文献类型：
--
作者：
V. Madhira;Peng Ren;O. Vechorkin;Xile Hu;David A. Vicic
以氟化铯和三甲基(五氟乙基)硅烷为原料，合成了一种含全氟乙基配体的双(氨基)酰胺镍钳配合物。电化学实验表明，LnI-C(2)F(5)络合物的氧化发生在与LnI-Cl衍生物相同的电位下，而LnI-C(2)F(5)络合物的还原发生在略高的正电位下。电化学数据的相似性被密度泛函理论(DFT)所证实，该理论预测LnI-C(2)F(5)和LnI-Cl的HOMO(HOMO=最高占据分子轨道)和Lumo(LUMO=最低未占据分子轨道)的能量在数量级上相等。密度泛函还表明，双(氨基)酰胺镍钳形配合物的基态主要是配体，而Lumo的主要性质是金属，支持该配体的氧化还原活性。
The synthesis of a bis(amino)amide nickel pincer complex bearing a perfluoroethyl ligand was effected by reaction of the corresponding nickel chloride complex with cesium fluoride and trimethyl(pentafluoroethyl)silane. Electrochemical experiments revealed that the oxidation of the LNi-C(2)F(5) complex occurs at the same potential as the LNi-Cl derivative, but reduction of the LNi-C(2)F(5) complex occurs at slightly more positive potentials. The similarity of the electrochemical data was corroborated by density functional theory (DFT), which predicts that the energies of the HOMOs (HOMO = highest occupied molecular orbital) and LUMOs (LUMO = lowest unoccupied molecular orbital) of the LNi-C(2)F(5) and LNi-Cl complexes are equal in magnitude. DFT also revealed that the HOMOs of the bis(amino)amide nickel pincer complexes are primarily ligand in character, while the LUMOs are predominantly metal in character, supporting redox-activity with this ligand.
影响因子：
2.8
作者：
Kieltsch, Iris;Dubinina, Galyna G.;Vicic, David A.
通讯作者：
Vicic, David A.