Synthesis and Structural Analysis of (Imido)Vanadium(V) Complexes Containing Chelate (Anilido)Methyl-imine Ligands: Ligand Effect in Ethylene Dimerization

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• 作者：Kotohiro Nomura ; Atsushi Igarashi ; Shohei Katao ; Wenjuan Zhang ; Wen-Hua Sun
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：March 4, 2013
• 年：2013
• 卷：52
• 期：5
• 页码：2607-2614
• 全文大小：428K
• 年卷期：v.52,no.5(March 4, 2013)
• ISSN：1520-510X

文摘

A series of (imido)vanadium dichlorido complexes containing chelate anionic donor ligands of the type, VCl₂(L)(NR) [R = 1-adamantyl (Ad), L = 2-(2,6-Me₂C₆H₃)NCH₂(C₉H₆N) (2), 8-(2,6-Me₂C₆H₃)NCH₂(C₉H₆N) (3); L = 2-(2,6-R鈥?sub>2C₆H₃)NCH₂(C₅H₄N), R = 2-MeC₆H₄, R鈥?= Me (4a), ⁱPr (4b); L = 2-(2,6-Me₂C₆H₃)NCH₂(C₅H₄N), R = 4-MeC₆H₄ (5), 3,5-Me₂C₆H₃ (6)], have been prepared and identified. The reactions with ethylene by 2,3 in the presence of methylaluminoxane (MAO) afforded a mixture of high molecular weight polyethylene and oligomers. Reactions with ethylene by VCl₂[2-(2,6-R鈥?sub>2C₆H₃)NCH₂(C₅H₄N)](NAd) (1a,b), 4鈥?b>6 afforded 1-butene with high selectivities (>92%), and the activities by 4a,b are at the same level as those in 1a,b. The activities by 5,6 were lower than 4a,b and were at the same level of that by VCl₂[2-(2,6-Me₂C₆H₃)NCH₂(C₅H₄N)](NPh). These results thus suggest that both the chelate anionic donor and the imido ligands play a role for both the activity and the selectivity.