Double Ligand Activation in Silyl-Substituted Rare-Earth Cyclobutadienyl Complexes
Double Ligand Activation in Silyl-Substituted Rare-Earth Cyclobutadienyl Complexes
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DOI：
10.1021/acs.organomet.9b00763
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发表时间：
2020-01-13
期刊：
影响因子：
2.8
通讯作者：
Layfield, Richard A.
中科院分区：
文献类型：
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作者：
Chakraborty, Anindita;Day, Benjamin M.;Layfield, Richard A.
环丁二烯(CB)试剂[Na-2{ETA(4)-C-4(SiMe3)(4)}(THF)](2)(2)(2)与稀土卤化物[MCl3(THF)(X)]反应，其中M=Y，Dy(x=3.5)和Lu(x=3)，给出了夹心配位聚合物[M{eta(3)-C-4(SiMe3)(4)H}{eta(4)-C-4(siMe(3))(3)-kappa-(CH(2)siMe(2)}Na](infinity)(3(M)，M=Y，Dy，Lu)]。稀土金属在3(M)中的配位环境是一个ETA(4)-环丁二烯配体，另外还有一个嵌入的三甲基硅基和一个ETA(3)-环丁烯配体。3(M)中晶场的轴向性质反映在3(Dy)的单分子磁性中，它在零磁场下具有309 cm(-1)的各向异性势垒。
The sodium cyclobutadienyl (Cb) reagent [Na-2{eta(4)-C-4(SiMe3)(4)}(THF)](2) (2) reacts with rare-earth halides [MCl3(THF)(x)], where M = Y, Dy (x = 3.5) and Lu (x = 3), giving the sandwich coordination polymers [M{eta(3)-C-4(SiMe3)(4)H}{eta(4) -C-4 (siMe(3))(3)-kappa-(CH(2)siMe(2)}Na](infinity) (3(M) , M = Y, Dy, Lu). The coordination environments of the rare-earth metals in 3(M) feature an eta(4)-cyclobutadienyl ligand, with additional coordination by a tuck-in trimethylsilyl group and an eta(3)-cyclobutenyl ligand. The ligand activation is thought to be a consequence of deprotonation of the Cb ligand by 2. The axial nature of the crystal field in 3(M) is reflected in the single-molecule magnet properties of 3(Dy), which has an anisotropy barrier of 309 cm(-1) in zero applied magnetic field.