Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization
Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization
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DOI：
10.1016/j.molcata.2006.03.008
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发表时间：
2006-07-01
影响因子：
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通讯作者：
Hu, Ning-Hai
中科院分区：
文献类型：
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作者：
Hu, Tao;Li, Yan-Guo;Hu, Ning-Hai
一系列双核中性镍、钯配合物[（XC6H2CH=NC6H3-iPr（2））MRL]（2）4b-f（X=NO2，M=Ni，R=Ph，L=PPh3，4b; X=H，M=Pd，R=Me，L=PPh3，4c; X=H，M=Pd，R=Me，L=Py，4d; X=NO2，M=Pd，R=Me，L=PPh3，4e; X=NO2，M=Pd，R=Me，L=Py，4f）和[（C10H7CH=NC6H3-iPr（2））MRL]（2）8a-c（M=Ni，R=Ph，L= PPh3，8a; M=Pd，R=Me，L= Py，8b; M=Pd，R=Me，L=Py，8c）。配合物4 e和8b的结构也通过X-射线晶体学分析得到证实。以改性甲基铝氧烷（MMAO）为助催化剂，这些配合物和配合物[（C6 H3CH = NC 6 H3-iPr（2））NiPh（PPh 3）]（2）4a能催化降冰片烯（NBE）的加成聚合，其活性高达2.3 × 10（8）g PNBE/（mol（M）h）。配合物的结构对降冰片烯聚合的催化活性有很大影响。用镍络合物获得的聚合物是可溶的，而用钯络合物获得的聚合物是不溶的。在相同条件下，含PPh 3配体的钯配合物4c、4 e和8b比相应的含吡啶配体的配合物4d、M和8 c表现出更高的活性。(c)2006 Elsevier B. V.保留所有权利。
A series of binuclear neutral nickel and palladium complexes [(XC6H2CH=NC6H3-iPr(2))MRL](2) 4b-f (X=NO2, M=Ni, R=Ph, L=PPh3, 4b; X=H, M=Pd, R=Me, L=PPh3,4c; X=H,M=Pd, R=Me, L=Py, 4d; X=NO2,M=Pd, R=Me, L=PPh3, 4e; X=NO2, M=Pd, R=Me, L=Py, 4f) and [(C10H7CH=NC6H3-iPr(2))MRL](2) 8a-c (M=Ni, R=Ph, L=PPh3, 8a; M=Pd, R=Me, L=PPh3, 8b; M=Pd, R=Me, L=Py, 8c) have been synthesized and characterized. The structures of complexes 4e and 8b have also been confirmed by X-ray crystallographic analysis. With modified methylalummoxane (MMAO) as cocatalysts, these complexes and complex [(C6H3CH=NC6H3-iPr(2))NiPh(PPh3)](2) 4a are capable of catalyzing the addition polymerization of norbomene (NBE) with the high activity up to 2.3 x 10(8) g PNBE/(mol(M) h). The structure of complexes affects considerably catalytic activity towards norbomene polymerization. The polymers obtained with nickel complexes are soluble, while those obtained with palladium complexes are insoluble. Palladium complexes 4c, 4e and 8b bearing PPh3 ligands exhibit much higher activities than the corresponding complexes 4d, M and 8c bearing pyridine ligands under the same conditions. (c) 2006 Elsevier B.V. All rights reserved.