Synthesis and Structural Analysis of (Imido) vanadium Dichloride Complexes Containing 2-(2 '-Benz-imidazolyl) pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization

doi:10.1021/acsomega.7b01225

	Synthesis and Structural Analysis of (Imido) vanadium Dichloride Complexes Containing 2-(2 '-Benz-imidazolyl) pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization
	Nomura, K ; Oshima, M ; Mitsudome, T ; Harakawa, H ; Hao, P ; Tsutsumi, K ; Nagai, G ; Ina, T ; Takaya, H ; Sun, WH
刊名	ACS OMEGA
	2017-12-01
卷号	2 期号:12 页码:8660-8673
ISSN号	2470-1343
DOI	10.1021/acsomega.7b01225
英文摘要	(Imido)vanadium(V) dichloride complexes containing 2-(2'-benzimidazolyl)-6-methylpyridine ligand (L) of type V(NR)Cl-2(L) [R = 1-adamantyl (Ad, 1), C6H5 (2), and 2,6-Me2C6H3 (3)] have been prepared, and their structures were determined by X-ray crystallography as distorted trigonal bipyramidal structures around vanadium. Reactions with ethylene using 1-3 in the presence of methylaluminoxane (MAO) afforded a mixture of oligomer and polymers, and the compositions were affected by the imido ligand employed. By contrast, 1-3 exhibited remarkable catalytic activities for ethylene polymerization in the presence of Me2AlCl; the phenylimido complex (2) exhibited the highest activity [80 100 kg-PE/mol-V.h turn over frequency (TOF, 2 850 000 h(-1), 792 s(-1))]. The ethylene copolymerizations with norbornene afforded ultrahigh-molecular-weight copolymers with uniform molecular weight distributions and compositions [e.g., M-n = 1.71-2.66 x 10(6), M-w/M-n = 2.27-2.53]. On the basis of V nuclear magnetic resonance (V-51 NMR), electron spin resonance, and V K-edge X-ray absorption near-edge structure (XANES) spectra of the catalyst solution, the observed difference in the catalyst performance in the presence of (between) MAO and Me2AlCl cocatalyst should be due to the formation of different catalytically active species with different oxidation states. Apparent changes in the oxidation state were observed in the (especially in the NMR and XANES) spectra upon addition of Me2AlCl, whereas no significant changes in the spectra were observed in presence of MAO.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000418744400013
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/41979]
专题	化学研究所_工程塑料实验室
作者单位	1.Nomura, K (reprint author), Tokyo Metropolitan Univ, Fac Sci & Engn, Dept Chem, 1-1 Minami Osawa, Hachioji, Tokyo 1920397, Japan. 2.Sun, WH (reprint author), Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China. 3.Mitsudome, T (reprint author), Osaka Univ, Dept Mat Engn Sci, 1-3 Machikaneyama, Toyonaka, Osaka 5608531, Japan. 4.Yamazoe, S (reprint author), Univ Tokyo, Dept Chem, Sch Sci, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1130033, Japan.
推荐引用方式 GB/T 7714	Nomura, K,Oshima, M,Mitsudome, T,et al. Synthesis and Structural Analysis of (Imido) vanadium Dichloride Complexes Containing 2-(2 '-Benz-imidazolyl) pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization[J]. ACS OMEGA,2017,2(12):8660-8673.
APA	Nomura, K.,Oshima, M.,Mitsudome, T.,Harakawa, H.,Hao, P.,...&Yamazoe, S.(2017).Synthesis and Structural Analysis of (Imido) vanadium Dichloride Complexes Containing 2-(2 '-Benz-imidazolyl) pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization.ACS OMEGA,2(12),8660-8673.
MLA	Nomura, K,et al."Synthesis and Structural Analysis of (Imido) vanadium Dichloride Complexes Containing 2-(2 '-Benz-imidazolyl) pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization".ACS OMEGA 2.12(2017):8660-8673.