Half-Sandwich Rare Earth Metal Complexes as Novel Catalysts for Olefin Polymerization and Other Chemical Transformations
Half-Sandwich Rare Earth Metal Complexes as Novel Catalysts for Olefin Polymerization and Other Chemical Transformations
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DOI：
10.1246/bcsj.20100003
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发表时间：
2010-05
影响因子：
4
通讯作者：
M. Nishiura;Z. Hou
中科院分区：
文献类型：
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作者：
M. Nishiura;Z. Hou
本文介绍了单（环戊二烯基）连接稀土金属烷基和氢化物配合物的合成和化学研究进展。采用三烷基稀土配合物与中性环戊二烯衍生物之间的烷烃消去反应或三氯化稀土与相应配体的碱金属盐的复化学反应制备了半夹心单、二烷基稀土配合物。二烷基配合物与硼酸盐的等价物如[Ph 3c][B(c6f5)4]或[phnme2h][B(c6f5)4]反应容易生成相应的阳离子单烷基物种，这些阳离子单烷基物种是多种烯烃聚合和共聚的优良催化剂，从而产生新的高分子材料家族，这些材料具有新颖的性能，但很难用其他催化剂制备。含有硅烯连接环戊二烯芳酰胺配体的半夹心单烷基稀土配合物对于催化末端炔的二聚化、末端炔与异氰酸酯的交叉偶联以及催化末端炔C-H、胺N-H和膦P-H键与碳二亚胺的加成具有优异的催化剂作用。二烷基稀土配合物的氢解反应得到了一类新的多核稀土金属多氢化物配合物，这些配合物在结构和反应活性上都具有独特的特点。
This article describes our recent studies on the synthesis and chemistry of mono(cyclopentadienyl)-ligated rare earth metal alkyl and hydride complexes. The half-sandwich mono- and dialkyl rare earth metal complexes are prepared either by alkane elimination reactions between trialkyl rare earth complexes and the neutral cyclopentadiene derivatives or by metathetical reactions of rare earth trichlorides with the alkali metal salts of the corresponding ligands. The reaction of the dialkyl complexes with an equivalent of a borate compound such as [Ph 3 C][B(C 6 F 5 )4] or [PhNMe 2 H][B(C 6 F 5 )4] generates easily the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a new family of polymer materials that show novel properties but are difficult to prepare by other catalysts. The half-sandwich monoalkyl rare earth complexes bearing the silylene-linked cyclopentadienyl-arylamido ligands act as excellent catalysts for the catalytic dimerization of terminal alkynes, cross coupling of terminal alkynes with isocyanides, and the catalytic addition of terminal alkyne C-H, amine N-H, and phosphine P-H bonds to carbodiimides. The hydrogenolysis of the dialkyl rare earth complexes with H 2 affords a new class of polynuclear rare earth metal polyhydride complexes, which show unique features in both structure and reactivity.