Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes
Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes
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DOI：
10.1021/om7008952
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发表时间：
2008-01
期刊：
影响因子：
2.8
通讯作者：
H. F. Yuen;T. Marks
中科院分区：
文献类型：
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作者：
H. F. Yuen;T. Marks
以无碱的Ln[N（SiHMe 2）2]3配合物为高效脱氨试剂，合成了双核稀土配合物p-双{η5-（2，3，4，5-四甲基）Ln[N（SiHMe 2）2]2}亚苯基[p-Ln 2]（Ln = Y，La，Lu）和m-双{η5-以相应的亚苯基连接的四甲基环戊二烯为原料合成了（2，3，4，5-四甲基取代）La[N（SiHMe 2）2]2}亚苯基[m-La 2]。所得产物用作新型多中心均相4f催化剂。反应性研究表明，这些双核有机镧系配合物有效地催化氨基烯烃、氨基炔和氨基二烯的分子内氢胺化/环化，在60 °C下的转换频率高达10 h−1。
Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclopentadienyl)Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln = Y, La, Lu) and m-bis{η5-(2,3,4,5-tetramethylcyclopentadienyl)La[N(SiHMe2)2]2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h−1 at 60 °C.