Xuyang Yan, Wentao Chen, Wang Xie, Xiuling Wang, Yat-Ming So, Xiaochao Shi
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引用次数: 0
摘要
我们合成了一系列双核稀土金属配合物,这些配合物含有新设计的烯酰胺恶唑酸配体,具有桥接对位苯基、偏苯基、1,5-萘基和 1,5-萘基等分子。核磁共振和 X 射线衍射分析证实了所获复合物的双核结构,其中两个烯氨基恶唑金属单元位于桥接芳基平面的反式位置。经 [Ph3C][B(C6F5)4] 活化后,所有稀土金属配合物均可作为异戊二烯聚合的高效催化剂,生成具有高顺式-1,4 规则性(高达 96.1%)和高分子量的聚合物。活性金属中心的立体效应和电子效应以及金属中心的半径是决定双核催化体系的催化活性和顺式-1,4 选择性的主要因素。与单核类似物相比,具有对位苯桥的双核钇催化体系在聚合过程中表现出更高的热稳定性和催化效率,揭示了该双核催化体系中的特殊双核效应。
Binuclear Enamino-Oxazolinate Rare-Earth Metal Complexes: Synthesis and Their Catalytic Performance in Isoprene Polymerization.
We have synthesized a series of binuclear rare-earth metal complexes bearing the newly designed enamino-oxazolinate ligands that feature bridging para-phenyl, meta-phenyl, 1,5-naphthalenyl, and 1,5-anthracenyl moieties. NMR and X-ray diffraction analyses confirmed the binuclear structures of the obtained complexes with two enamino-oxazolinate-metal units located at a trans position against the bridged aryl plane. After activation by [Ph3C][B(C6F5)4], all the rare-earth metal complexes served as efficient catalysts for isoprene polymerization, producing polymers with high cis-1,4 regularity (up to 96.1%) and high molecular weight. The steric and electronic effects exerted on the active metal centers, as well as the radius of metal centers, were the major contributing factors for determining both the catalytic activity and cis-1,4-selectivity of the binuclear catalytic systems. Compared to its mononuclear analogue, the binuclear yttrium catalytic system with a para-phenyl bridge exhibited a higher thermostability and catalytic efficiency during polymerization, revealing a special binuclear effect in this binuclear catalytic system.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.