含有(2-苯甲酰基甲基)吡啶配体的(亚氨基)钒配合物高效二聚乙烯：对活性和选择性有显著配体效应。

Highly efficient dimerization of ethylene by (imido)vanadium complexes containing (2-anilidomethyl)pyridine ligands: notable ligand effect toward activity and selectivity.

机构信息

Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0101, Japan.

出版信息

J Am Chem Soc. 2010 Apr 7;132(13):4960-5. doi: 10.1021/ja100573d.

DOI:10.1021/ja100573d

PMID:20218571

Abstract

(Imido)vanadium(V) complexes containing the (2-anilidomethyl)pyridine ligand, V(NR)Cl(2)[2-ArNCH(2)(C(5)H(4)N)] (R = 1-adamantyl (Ad), cyclohexyl (Cy), phenyl), exhibit remarkably high catalytic activities (e.g. TOF = 2 730 000 h(-1) (758 s(-1)) by V(NAd)Cl(2)[2-(2,6-Me(2)C(6)H(3))NCH(2)(C(5)H(4)N)) 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 (polymerization vs dimerization), and the electronic nature directly affects the catalytic activity (activity: R = Ad > Cy > Ph).

摘要

含有（2-亚胺基甲基）吡啶配体的（亚氨基）钒（V）配合物，V（NR）Cl（2）[2-ArNCH（2）（C（5）H（4）N）]（R=1-金刚烷基（Ad）、环己基（Cy）、苯基），表现出极高的催化活性（例如，在 MAO 的存在下，V（NAd）Cl（2）[2-（2,6-Me（2）C（6）H（3））NCH（2）（C（5）H（4）N）]对于乙烯的二聚化，TOF=2730000h（-1）（758s（-1）），仅得到 1-丁烯（选择性 90.4%至>99%）。亚胺配体的空间位阻在选择性（聚合与二聚）中起着重要作用，而电子性质直接影响催化活性（活性：R=Ad>Cy>Ph）。