Syntheses of bis- and tetra(trimethylsilyl) substituted lanthanocene methyl complexes and their catalyses for polymerizations of methyl methacrylate, ε-caprolactone and L-lactide

被引:35
作者
Satoh, Y [1 ]
Ikitake, N [1 ]
Nakayama, Y [1 ]
Okuno, S [1 ]
Yasuda, H [1 ]
机构
[1] Hiroshima Univ, Grad Sch Engn, Dept Appl Chem, Higashihiroshima 7398527, Japan
关键词
methyl methacrylate; epsilon-caprolactone; L-lactide; trimethylsilyl substituted samarocene methyl; neodocene methyl; living polymerizations; samarocene methyl;
D O I
10.1016/S0022-328X(02)02124-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Bis- and tetra(trimethylsilyl) substituted lanthanocene methyl complexes, [(Me3SiC5H4)(2)SmMe](2) (2) {[1,3-(Me-3-Si)(2)C5H3](2)SmMe}(2) (4) and {[1,3(Me3Si)(2)C5H3](2)NdMe}(2) (5) were prepared in high yield from trimethylsilyl- or bis(trimethylsilyl)cyclopentadienyllithium and LnCl(3)(THF)(2) followed by the reaction with a stoichiometric amount of MeLi. The molecular structures of 2 and 4 as well as their precursors, [(Me3SiC5H4)(2)SmCl](2) (1) and [1,3-(Me-3,Si)(2)C5H3](2)SmCl2Li(THF)(2) (3) were determined by X-ray crystallographic analyses. The complexes 2, 4 and 5 perform the living polymerization of methyl methacrylate and the block copolymerizations Of L-lactide with epsilon-caprolactone in high yields in the absence of any cocatalysts. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:42 / 52
页数:11
相关论文
共 29 条
[11]   Synthesis and olefin polymerization catalysis of new trivalent samarium and yttrium complexes with bridging bis(cyclopentadienyl) ligands [J].
Ihara, E ;
Yoshioka, S ;
Furo, M ;
Katsura, K ;
Yasuda, H ;
Mohri, S ;
Kanehisa, N ;
Kai, Y .
ORGANOMETALLICS, 2001, 20 (09) :1752-1761
[12]   LIVING POLYMERIZATIONS AND COPOLYMERIZATIONS OF ALKYL ACRYLATES BY THE UNIQUE CATALYSIS OF RARE-EARTH-METAL COMPLEXES [J].
IHARA, E ;
MORIMOTO, M ;
YASUDA, H .
MACROMOLECULES, 1995, 28 (23) :7886-7892
[13]   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
[14]   HIGHLY REACTIVE ORGANOLANTHANIDES - SYSTEMATIC ROUTES TO AND OLEFIN CHEMISTRY OF EARLY AND LATE BIS(PENTAMETHYLCYCLOPENTADIENYL) 4F HYDROCARBYL AND HYDRIDE COMPLEXES [J].
JESKE, G ;
LAUKE, H ;
MAUERMANN, H ;
SWEPSTON, PN ;
SCHUMANN, H ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (26) :8091-8103
[15]   SYNTHESIS AND CHARACTERIZATION OF STABLE ANIONIC GROUP-3A DICHLOROMETALLOCENE(III) COMPLEXES AND THE X-RAY STRUCTURE OF [ASPH4][ND[ETA-C5H3(SIME3)2]2CL2] [J].
LAPPERT, MF ;
SINGH, A ;
ATWOOD, JL ;
HUNTER, WE ;
ZHANG, HM .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1983, (02) :69-70
[16]   ORGANO-METALLIC COMPLEXES OF THE GROUP-3A AND LANTHANOID METALS CONTAINING M(MU-CL)2LI BRIDGING UNITS - THE X-RAY STRUCTURE OF [ND(ETA-[C5H3(SIME3)2])2(MU-CL)2LI(THF)2] (THF=TETRAHYDROFURAN) [J].
LAPPERT, MF ;
SINGH, A ;
ATWOOD, JL ;
HUNTER, WE .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (22) :1191-1193
[17]   USE OF THE "BIS(TRIMETHYLSILYL)CYCLOPENTADIENYL LIGAND FOR STABILIZING EARLY (F0-F3) LANTHANOCENE CHLORIDES - X-RAY STRUCTURE OF [(PR(ETA-[C5H3(SIME3)2])2CL)2] AND OF ISOLEPTIC SCANDIUM AND YTTERBIUM COMPLEXES [J].
LAPPERT, MF ;
SINGH, A ;
ATWOOD, JL ;
HUNTER, WE .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (22) :1190-1191
[18]  
Pope M.T., 1983, HETEROPOLY ISOPOLY O
[19]   ORGANOMETALLIC COMPOUNDS OF THE LANTHANIDES .42. BIS(DIMETHOXYETHANE)LITHIUM BIS(CYCLOPENTADIENYL)BIS(TRIMETHYLSILYL)LANTHANIDE COMPLEXES [J].
SCHUMANN, H ;
NICKEL, S ;
LOEBEL, J ;
PICKARDT, J .
ORGANOMETALLICS, 1988, 7 (09) :2004-2009
[20]  
SHELDRICK GM, 1994, PROGRAM SOLUTION CRY