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

doi:10.1021/om300263p

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	Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization
	Jian, Zhongbao 2,3; Petrov, Alex R.1; Hangaly, Noa K.1; Li, Shihui 2; Rong, Weifeng 2,3; Mou, Zehuai 2,3; Rufanov, Konstantin A.1,4; Harms, Klaus 1; Sundermeyer, Joerg 1; Cui, Dongmei 2
刊名	ORGANOMETALLICS
	2012-06-11
卷号	31 期号:11 页码:4267-4282
ISSN号	0276-7333
DOI	10.1021/om300263p
英文摘要	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.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000304978700023
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/49789]
专题	中国科学院化学研究所
通讯作者	Sundermeyer, Joerg
作者单位	1.Univ Marburg, Fachbereich Chem, D-35032 Marburg, Germany 2.Chinese Acad Sci, State Key Lab Polymer Phys & Chem, Changchun Inst Appl Chem, Changchun 130022, Peoples R China 3.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China 4.MV Lomonosov Univ Moscow, Dept Chem, Moscow 119992, Russia
推荐引用方式 GB/T 7714	Jian, Zhongbao,Petrov, Alex R.,Hangaly, Noa K.,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, Zhongbao.,Petrov, Alex R..,Hangaly, Noa K..,Li, Shihui.,Rong, Weifeng.,...&Cui, Dongmei.(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, Zhongbao,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.