Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization

	Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization
	Jian ZB ; Petrov AR ; Hangaly NK ; Li SH ; Rong WF ; Mou ZH ; Rufanov KA ; Harms K ; Sundermeyer J ; Cui DM
刊名	organometallics
	2012
卷号	31 期号:11 页码:4267-4282
关键词	CONSTRAINED-GEOMETRY COMPLEXES ALPHA-OLEFIN POLYMERIZATION SYNDIOSPECIFIC STYRENE POLYMERIZATION N-HETEROCYCLIC CARBENE SANDWICH COMPLEXES TRANSITION-METAL LINKED CYCLOPENTADIENYL ETHENE POLYMERIZATION METALLOCENE CATALYSTS LANTHANIDE COMPLEXES
ISSN号	0276-7333
通讯作者	sundermeyer j
中文摘要	treatment of ln(ch2sime3)(3)(thf)(2) (ln = sc, y, and lu) with 1 equiv of cppn-type ligands c5h4=pph2-nh-c6h3r2 (r = me, l-1(me); r = pr-i, l-1(pr-i)) at room temperature readily generated the corresponding cppn-type bis(alkyl) complexes 1 and 2a-2c. addition of 3 equiv of lich2sime3 to a mixture of l-1(pr-i) and lncl(3)(thf)(2) (ln = sm and nd) also afforded the cppn-type bis(alkyl) complexes 2d and 2e. the cp moiety bonds to the central metal in a classical eta(5) mode in all cppn-type complexes 1 and 2. in contrast, the (cppn)-p-me-type ligands c5me4h-pph2=n-c6h3r2 (r = me, l-2(me); r = pr-i, l-2(pr-i)) behaved differently. l-2(me) did not react with sc(ch2sime3)(3)(thf)(2). similarly, l-2(pr-i) was also inert to sc(ch2sime3)(3)(thf)(2) even at 50 degrees c. when the central metal was changed to yttrium, however, the equimolar reaction between y(ch2sime3)(3)(thf)(2) and l-2(pr-i) in the presence of licl afforded two bis(alkyl) complexes 3a and 3b. in the main product 3a, [c5hme3(eta(3)-ch2)-pph2=n-(c6h3pr2)-pr-i]y(ch2sime3)(2)(thf), the ligand bonds to the y3+ ion in a rare eta(3)-allyl/kappa-n mode, whereas in 3b, (c5me4-pph2=n-(c6h3pr2)-pr-i)y(ch2sime3)(2)(licl)(thf), the cp ring coordinates to the y3+ ion in an eta(5) mode, and a licl unit is located between the y3+ ion and the nitrogen atom. when the central metal was changed to lutetium, a bis(alkyl) complex 4a, [c5hme3(eta(3)-ch2)-pph2=n-(c6h3pr2)-pr-i]lu(ch2sime3)(2)(thf), and a bis(alkyl) complex 4b, (c5me4-pph2=n-(c6h3pr2)-pr-i)lu(ch2sime3)(2), were isolated. the protonolysis reaction of the indpn-type ligands c9f7-pph2=n-c6h3r2 (r = me, l-3(me); r = et, l-3(et); r = pr-i, l-3(pr-i)) with ln(ch2sime3)(3)(thf)(2) (ln = sc, y, and lu) generated the indpn-type bis(alkyl) complexes 5a-5c, 6, and 7a-7c, selectively, where the ind moiety tends to adopt an eta(3)-bonding fashion. the more bulky flupn-type ligands c13h9-pph2=n-c6h4r (r = h, l-4(h); r = me, l-4(me)) were treated with ln(ch2sime3)(3)(thf)(2) (ln = sc and lu) to afford the flupn-type bis(alkyl) complexes 8 and 9a and 9b, where the flu moiety has a rare eta(1)-bonding mode. complexes 1-9 were fully characterized by h-1, c-13, and p-31 nmr; x-ray; and elemental analyses. upon activation with alr3 and [ph3c][b(c6f5)(4)], the scandium complexes showed good to high catalytic activity for ethylene polymerization. the effects of the sterics and electronics of the ligand, the loading and the type of alr3, the polymerization temperature, and the polymerization time on the catalytic activity were also discussed.
收录类别	SCI收录期刊论文
语种	英语
WOS记录号	WOS:000304978700023
公开日期	2013-05-20
内容类型	期刊论文
源URL	[http://ir.ciac.jl.cn/handle/322003/48102]
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,Petrov AR,Hangaly NK,et al. Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization[J]. organometallics,2012,31(11):4267-4282.
APA	Jian ZB.,Petrov AR.,Hangaly NK.,Li SH.,Rong WF.,...&Cui DM.(2012).Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization.organometallics,31(11),4267-4282.
MLA	Jian ZB,et al."Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization".organometallics 31.11(2012):4267-4282.