(Imido)vanadium Complexes as Efficient Catalyst Precursors for Olefin Polymerization/Oligomerization
(Imido)vanadium Complexes as Efficient Catalyst Precursors for Olefin Polymerization/Oligomerization
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DOI：
10.1007/s10563-011-9116-x
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发表时间：
2011-02
影响因子：
3
通讯作者：
Shu Zhang;K. Nomura
中科院分区：
文献类型：
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作者：
Shu Zhang;K. Nomura
含有V（NAr）Cl 2（L）（Ar = 2，6-Me 2 C 6 H 3，L =芳氧基、酮酰亚胺苯氧基亚胺等）型阴离子辅助给体配体的（芳基酰亚胺基）钒（V）配合物，在Al助催化剂存在下，催化剂对乙烯聚合具有较高的催化活性; V（NAr）Cl2（O-2，6-Me_2C_6H_3）在卤代烷基铝（如Et_2AlCl、EtAlCl_2等）存在下表现出极高的催化活性。（芳基亚氨基）钒（V）-亚烷基配合物，V（CHSiMe 3）（NAr）（L′）（L′ = N= CtBu 2，O-2，6-iPr 2C 6 H3）催化剂对异戊二烯的开环易位聚合具有显著的催化活性。以2-苯胺基甲基吡啶为配体的（亚氨基）钒（V）配合物V（NR）Cl 2 [2-Ar′ NCH 2（C5 H4 N）]（R = 1-金刚烷基、环己基、苯基，Ar′ = 2，6-Me 2C 6 H3，2，6-iPr 2C 6 H3）在MAO存在下对乙烯二聚反应表现出显著的催化活性，只生成1-丁烯（选择性90.4 ~>99%）.亚氨基配体的空间位阻对选择性起着重要作用，而电子性质直接影响活性。
(Arylimido)vanadium(V) complexes containing anionic ancillary donor ligands of type, V(NAr)Cl2(L) (Ar = 2,6-Me2C6H3, L = aryloxo, ketimide phenoxyimine, etc.) exhibited high catalytic activities for ethylene polymerization in the presence of Al cocatalyst; V(NAr)Cl2(O-2,6-Me2C6H3) showed the exceptionally high activities in the presence of halogenated Al alkyls such as Et2AlCl, EtAlCl2, etc. (Arylimido)vanadium(V)-alkylidene complexes, V(CHSiMe3)(NAr)(L′) (L′ = N=CtBu2, O-2,6-iPr2C6H3) exhibited the remarkable catalytic activities for ring-opening metathesis polymerization of norbornene. (Imido)vanadium(V) complexes containing the (2-anilidomethyl)pyridine ligand, V(NR)Cl2[2-Ar′NCH2(C5H4N)] (R = 1-adamantyl, cyclohexyl, phenyl, Ar′ = 2,6-Me2C6H3, 2,6-iPr2C6H3), exhibit the remarkable activities for ethylene dimerization in the presence of MAO, affording 1-butene exclusively (selectivity 90.4 to >99%). The steric bulk of the imido ligand plays an important role in the selectivity, and the electronic nature directly affects the activity.