Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor.
Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor.
复制标题
由具有芳烃锚的三足 Tris(amido) 配体系统支持的稀土金属配合物。
作者：
Tiansi Xin;Xinrui Wang;Kexin Yang;Jiefeng Liang;Wenliang Huang
提出了一种新的以芳烃为锚的三脚架三酰胺配体体系，并将其应用于稀土金属的配位化学。两个三（酰胺基）配体与1，3，5-三苯基苯骨架制备在两个步骤中从商业上可获得的试剂在克规模。利用盐复分解和烷烃消除反应以中等至良好的产率制备单核稀土金属配合物。对于盐复分解反应，虽然金属三溴化物产生中性金属三（酰胺基）络合物，金属三氯化物导致形成酯络合物与结合到金属中心的额外的氯化物。通过X射线晶体学、元素分析、1H和13 C核磁共振谱对新化合物进行了表征。稀土金属络合物在固态下表现出[MN 3]片段的三角平面配位几何形状，而不是通常在稀土金属三（酰氨基）络合物如M[N（SiMe 3）2]3中观察到的三角锥体几何形状。此外，三脚架配体的芳烃锚与稀土金属离子进行不可忽略的相互作用。通过密度泛函理论计算，深入研究了三脚架配体与稀土金属离子之间的成键相互作用。虽然这些稀土金属配合物的LUMO主要是芳烃的π* 轨道，少量是金属基轨道，但镧配合物的HOMO-15和HOMO-16表明芳烃锚作为三价镧离子的π供体。
A new tripodal tris(amido) ligand system featuring an arene anchor was developed and applied to the coordination chemistry of rare earth metals. Two tris(amido) ligands with a 1,3,5-triphenylbenzene backbone were prepared in two steps from commercially available reagents on a gram scale. Salt metathesis and alkane elimination reactions were exploited to prepare mononuclear rare earth metal complexes in moderate to good yields. For salt metathesis reactions, while metal tribromides yielded neutral metal tris(amido) complexes, metal trichlorides led to the formation of ate complexes with an additional chloride bound to the metal center. The new compounds were characterized by X-ray crystallography, elemental analysis, and 1H and 13C nuclear magnetic resonance spectroscopy. The rare earth metal complexes exhibit a trigonal planar coordination geometry for the [MN3] fragment in the solid state rather than a trigonal pyramidal geometry, commonly observed for rare earth metal tris(amido) complexes such as M[N(SiMe3)2]3. Moreover, the arene anchor of the tripodal ligands is engaged in a nonnegligible interaction with the rare earth metal ions. Density functional theory calculations were performed to gain insight into the bonding interactions between the tripodal ligands and the rare earth metal ions. While LUMOs of these rare earth metal complexes are mainly π* orbitals of the arene with a minor component of metal-based orbitals, HOMO-15 and HOMO-16 of a lanthanum complex show that the arene anchor serves as a π donor to the trivalent lanthanum ion.
登录
查看更多内容
合成单位Fe氮酶：高离职率，冻结（57）feMössbauer数据和氢化物静止状态。
影响因子：
15
作者：
Del Castillo TJ;Thompson NB;Peters JC
通讯作者：
Peters JC
影响因子：
15
作者：
Kinzel T;Zhang Y;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
15
作者：
Creutz SE;Peters JC
通讯作者：
Peters JC
影响因子：
15
作者：
Castro-Rodriguez, I;Olsen, K;Meyer, K
通讯作者：
Meyer, K
影响因子：
4.6
作者：
Del Castillo TJ;Thompson NB;Suess DL;Ung G;Peters JC
通讯作者：
Peters JC