Synthesis of linked half sandwich rare-earth metal chlorido and borohydrido complexes and their catalytic behavior towards MMA polymerization

	Synthesis of linked half sandwich rare-earth metal chlorido and borohydrido complexes and their catalytic behavior towards MMA polymerization
	Jian ZB ; Zhao W ; Liu XL ; Chen XS ; Tang T ; Cui DM
刊名	dalton transactions
	2010
卷号	39 期号:29 页码:6871-6876
关键词	RING-OPENING POLYMERIZATION STEREOSPECIFIC ISOPRENE POLYMERIZATION ALPHA-OLEFIN POLYMERIZATION N-HETEROCYCLIC CARBENE RAY CRYSTAL-STRUCTURES METHYL-METHACRYLATE EPSILON-CAPROLACTONE STRUCTURAL-CHARACTERIZATION LIVING POLYMERIZATIONS MOLECULAR-STRUCTURES
ISSN号	1477-9226
通讯作者	cui dm
中文摘要	a series of rare-earth metal complexes attached by an amino-functionalized cyclopentadienyl ligand (c5me4h-c6h4-o-nme2) (1) was prepared. the metathesis reaction of the ligand lithium salt [c5me4h-c6h4-o-nme2]li with lncl(3)(thf)(n) afforded the dichlorido complexes [(c5me4h-c6h4-o-nme2)(2)ln(2)cl(4)][licl(thf)(2)] (ln = y (2a), lu (2b)), which are trinuclear connected by mu(3)-cl and mu(2)-cl multiple bridges. the straightforward metathesis reaction of ln(bh4)(3)(thf)(n) with equimolar [c5me4h-c6h4-o-nme2]li in thf medium yielded the first linked half sandwich ligand stabilized thf-free rare-earth metal bis(borohydrido) complexes (c5me4h-c6h4-o-nme2)ln(bh4)(2) (ln = sc (3a), sm (3b)), respectively. the single component borohydrido complex 3a showed high activity towards the bulk polymerization of methyl methacrylate without specific control, which showed high iso-selectivity (mm = 80%) when the polymerization was performed in benzene medium, and switched to syndio-selectivity (rr = 74% at -20 degrees c) in polar thf medium, whilst the metal chlorido species was inert. the binary catalyst system of 3a/(mgbu2)-bu-n had similar catalytic performances when compared with 3a in thf medium, but provided enriched syndio-control in benzene solution that was in contrast to the iso-control of 3a. surprisingly, 3a upon activation with (buli)-bu-n displayed an extremely high activity (1.1 x 10(6) g mol(sc)(-1) h(-1)) and afforded syndiotactic pmma (rr = 75%) at low polymerization temperature (-20 degrees c) in thf.
收录类别	SCI收录期刊论文
语种	英语
WOS记录号	WOS:000279913100040
公开日期	2012-04-26
内容类型	期刊论文
源URL	[http://ir.ciac.jl.cn/handle/322003/43605]
专题	长春应用化学研究所_长春应用化学研究所知识产出_期刊论文
推荐引用方式 GB/T 7714	Jian ZB,Zhao W,Liu XL,et al. Synthesis of linked half sandwich rare-earth metal chlorido and borohydrido complexes and their catalytic behavior towards MMA polymerization[J]. dalton transactions,2010,39(29):6871-6876.
APA	Jian ZB,Zhao W,Liu XL,Chen XS,Tang T,&Cui DM.(2010).Synthesis of linked half sandwich rare-earth metal chlorido and borohydrido complexes and their catalytic behavior towards MMA polymerization.dalton transactions,39(29),6871-6876.
MLA	Jian ZB,et al."Synthesis of linked half sandwich rare-earth metal chlorido and borohydrido complexes and their catalytic behavior towards MMA polymerization".dalton transactions 39.29(2010):6871-6876.