Macrocyclic Binucleating β-Diketiminate Ligands and their Lithium, Aluminum, and Zinc Complexes.
Macrocyclic Binucleating β-Diketiminate Ligands and their Lithium, Aluminum, and Zinc Complexes.
复制标题
大环双核β-Diketiminate 配体及其锂、铝和锌配合物。
DOI：
10.1021/om0700258
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发表时间：
2007
期刊：
影响因子：
2.8
通讯作者：
Holland,PatrickL
中科院分区：
文献类型：
--
作者：
Vela,Javier;Zhu,Liwei;Flaschenriem,ChristineJ;Brennessel,WilliamW;Lachicotte,ReneJ;Holland,PatrickL
将刚性芳香族连接物结合到β-diketiminate配体中，创建了一种双核支架，将两种金属保持在彼此附近。本文介绍了具有间位取代二甲苯间隔物的mBin2-和具有对位取代二甲苯间隔物的pBin2-的合成、表征和反应活性。分离了每个配体的锂、铝和锌的络合物，并在某些情况下用X射线结晶学进行了表征。锂配合物配位到溶剂衍生的四氢呋喃配体，而锌和铝配合物有烷基配体。MBin2-配体的络合物具有反构象，其中金属位于大环的相反侧，而pBin2-络合物则倾向于SYN构象。~1H核磁共振谱表明，锂络合物的构象转换较快，而锌、铝络合物的构象转换较慢。
The incorporation of rigid aromatic linkers into β-diketiminate ligands creates a binucleating scaffold that holds two metals near each other. This paper discloses the synthesis, characterization, and reactivity of mBin2-, which has a meta-substituted xylylene spacer, and pBin2-, which has a para-substituted xylylene spacer. Lithium, aluminum, and zinc complexes of each ligand have been isolated, and in some cases characterized by X-ray crystallography. The lithium complexes are coordinated to solvent-derived THF ligands, while the zinc and aluminum complexes have alkyl ligands. Complexes of the mBin2-ligand have an anti conformation in which the metals are on opposite sides of the macrocycle, while pBin2-complexes prefer a syn conformation. The1H NMR spectra of the complexes demonstrate that the conformations interconvert rapidly in the lithium complexes and less rapidly in the zinc and aluminum complexes.