Neodymium(III) complexes with bulky ansa-bis(cyclopentadienyl) ligands:: Synthesis and use in olefin oligomerization

被引：36

作者：

Bogaert, S

Chenal, T

Mortreux, A

Nowogrocki, G

Lehmann, CW

Carpentier, JF

机构：

[1] ENSCL, CNRS, UPRESA 8010, Lab Catalyse Lille, F-59652 Villeneuve Dascq, France

[2] ENSCL, CNRS, UPRESA 8012, Lab Cristallochim & Physicochim Solide, F-59652 Villeneuve Dascq, France

[3] Max Planck Inst Kohlenforsch, D-45466 Mulheim, Germany

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 01期

关键词：

D O I：

10.1021/om0006357

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The trivalent neodymium complexes [rac-{Me2Si(eta (5)-2-SiMe3-4-t-Bu-C5H2)(2))Nd(mu -Cl)(2)Li(THF)(2)] (rac-3),[rac-{Me2Si(eta (5)-2,4-(SiMe3)(2)C5H2)(2)}Nd(mu -Cl)(2)Li(THF)(2)] (rac-5), and [(Me2Si(eta (5)-2,4-(SiMe3)(2)C5H2)((eta (5)-3,4-(SiMe3)(2)C5H2)}Nd(mu -Cl)(2)Li(THF)(2)] (C-1-6) have been prepared and their structures investigated by NMR and X-ray crystallography. These new chlorolanthanocenes, when combined in situ with a dialkylmagnesium cocatalyst, initiate the polymerization of ethylene and 1-octene to yield di(oligoalkyl)magnesium species, which can be finally hydrolyzed to oligomers. Bulky bridged complexes rac-3, rac-5, and C-1-6 gave significantly more active catalysts for 1-octene oligomerization (M-n = 400-1300, M-w/M-n = 1.11-1.65) than systems based on nonbridged complexes [(eta (5)-C5Me5)(2)Nd(mu -Cl)(2)Li(Et2O)(2)] (1) and [(eta (5)-1,3-(SiMe3)(2)C5H3)(2)Nd(mu -Cl)(2)Li(THF)(2)] (7). Ethylene oligomerization (M-n = 400-5000) was best achieved with complexes 1 and rac-3, as important catalyst decay occurred with bridged bis(trimethylsilyl) systems rac-5 and C-1-6.

引用

收藏

页码：199 / 205

页数：7

相关论文

共 60 条

[11]

Edelmann F. T., 1996, TOP CURR CHEM, V179, P247

[12] C2-symmetric ansa-lanthanidocene complexes.: Synthesis via silylamine elimination and β-SiH agostic rigidity [J].

Eppinger, J ;

Spiegler, M ;

Hieringer, W ;

Herrmann, WA ;

Anwander, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (13) :3080-3096

[13] Synthesis, structure, and reactivity of peralkylcyclopentadienyl ansa-metallocenes of samarium:: Effect of steric crowding on the reactivity of tris(peralkylcyclopentadienyl)samarium complexes [J].

Evans, WJ ;

Cano, DA ;

Greci, MA ;

Ziller, JW .

ORGANOMETALLICS, 1999, 18 (08) :1381-1388

[14] REACTIVITY OF (C5ME5)2SM AND RELATED SPECIES WITH ALKENES - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A SERIES OF ORGANOSAMARIUM ALLYL COMPLEXES [J].

EVANS, WJ ;

ULIBARRI, TA ;

ZILLER, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (06) :2314-2324

[15] CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - SYNTHESIS, CHARACTERIZATION, AND CONFIGURATIONAL INTERCONVERSIONS OF CHIRAL, C-1-SYMMETRICAL ORGANOLANTHANIDE HALIDES, AMIDES, AND HYDROCARBYLS [J].

GIARDELLO, MA ;

CONTICELLO, VP ;

BRARD, L ;

SABAT, M ;

RHEINGOLD, AL ;

STERN, CL ;

MARKS, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10212-10240

[16] Synthesis, structure, and catalytic reactions of 1,2-bis(indenyl)ethane-derived lanthanocenes [J].

Gilbert, AT ;

Davis, BL ;

Emge, TJ ;

Broene, RD .

ORGANOMETALLICS, 1999, 18 (11) :2125-2132

[17] Synthesis and structure of ansa-metallocene complexes (M = ZrCl2, TiCl2, YCl, and LuCl) containing the bis(2-methyl-4,5,6,7-tetrahydroinden-yl)dimethylsilane ligand [J].

Halterman, RL ;

Schumann, H ;

Dübner, F .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 604 (01) :12-19

[18] Lanthanocene chemistry with [CpR]-, [Cpt]-, [Cptt]-, and [CpR′2SiMe2]2- ligands:: Synthesis and characterization of bis(cyclopentadienyl)lanthanide(III) halides and bis(cyclopentadienyl)lanthanide(II) complexes and crystal structures of [{NdCpR2(μ-Cl)}2], [{TmCptt2(μ-I)}2], and [Yb(CpR′2SiMe2)(THF)2] (CpR = η5-C5H4{CH(SiMe3)2}, Cpt = η5-C5H4(SiMe2But), Cptt = η5-C5H3(SiMe2But)2-1,3, and CpR′ = η5-C5H3{CH(SiMe3)2}-3) [J].

Hitchcock, PB ;

Lappert, MF ;

Tian, S .

ORGANOMETALLICS, 2000, 19 (17) :3420-3428

[19] Single site polymerization of ethylene and 1-olefins initiated by rare earth metal complexes [J].

Ihara, E ;

Nodono, M ;

Yasuda, H ;

Kanehisa, N ;

Kai, Y .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1996, 197 (06) :1909-1917

[20] Synthesis and olefin polymerization catalysis of new bivalent samarium complexes with bridging bis(cyclopentadienyl) ligands [J].

Ihara, E ;

Nodono, M ;

Katsura, K ;

Adachi, Y ;

Yasuda, H ;

Yamagashira, M ;

Hashimoto, H ;

Kanehisa, N ;

Kai, Y .

ORGANOMETALLICS, 1998, 17 (18) :3945-3956

← 1 2 3 4 5 6 →