LII.: Synthesis and characterization of bis- and mono-(η3-allyl)neodymium(III) chloride, Nd(η3-C3H5)2Cl•1.5 THF and Nd(η3-C3H5)Cl2•2THF, for preparation of highly active and selective complex catalysts for 1,4-cis-polymerization of butadiene

被引:37
作者
Maiwald, S
Taube, R
Hemling, H
Schumann, H
机构
[1] Tech Univ Munchen, Inst Anorgan Chem, Lehrstuhl Anorgan Chem, D-85747 Garching, Germany
[2] Universitat Halle Wittenberg, Inst Anorgan Chem, D-06217 Merseburg, Germany
[3] Tech Univ Berlin, Inst Anorgan Chem, D-10623 Berlin, Germany
关键词
allyl; catalysis; butadiene; neodym; polymerization;
D O I
10.1016/S0022-328X(97)00572-X
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The title complexes are obtainable by comproportionation reaction from Nd(eta(3)-C3H5)(3).Dioxan and NdCl3 . 2THF in the correspond ing molar ratio in tetrahydrofuran (THF) in very good yields. The characterization was done by elementary analysis, IR and H-1 NMR spectroscopy and for the bis(eta(3)-allyl) complex also by X-ray crystal structure analysis. In combination with methylaluminoxane (MAO) both complexes catalyze the 1.4-cis-polymerization of butadiene in toluene and heptane, respectively, with an extremely high activity and a selectivity up to 98%. The catalyst formation results from anion transfer to the Lewis-acid methylaluminoxane giving a cationic mono(eta(3)-allyl)neodymium(III) fragment, which is stabilized by coordinative interactions with the complex counter anion. (C) 1998 Elsevier Science S.A.
引用
收藏
页码:195 / 204
页数:10
相关论文
共 32 条
[1]  
BIAGINI P, 1995, NEW J CHEM, V19, P713
[2]  
Brintzinger H. H., 1995, ANGEW CHEM, V107, P1255
[3]   STEREOSPECIFIC OLEFIN POLYMERIZATION WITH CHIRAL METALLOCENE CATALYSTS [J].
BRINTZINGER, HH ;
FISCHER, D ;
MULHAUPT, R ;
RIEGER, B ;
WAYMOUTH, RM .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (11) :1143-1170
[4]   THE SYNTHESIS AND NUCLEAR-MAGNETIC-RESONANCE INVESTIGATION OF THE STRUCTURE AND CHEMICAL-DYNAMICS OF NEW ANIONIC TETRA-ALLYL COMPLEXES OF LANTHANIDE IONS [J].
BRUNELLI, M ;
POGGIO, S ;
PEDRETTI, U ;
LUGLI, G .
INORGANICA CHIMICA ACTA, 1987, 131 (02) :281-285
[5]  
Deacon G.B., 1996, J ORGANOMET CHEM, V511, P1
[6]   ORGANOMETALLIC CONFORMATIONAL EQUILIBRIA .10. STERIC FACTORS AND THEIR MECHANISTIC IMPLICATIONS IN PI-ALLYL(AMINE)CHLOROPALLADIUM(II) COMPLEXES [J].
FALLER, JW ;
THOMSEN, ME ;
MATTINA, MJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (11) :2642-&
[7]   3-COORDINATE ALUMINUM IS NOT A PREREQUISITE FOR CATALYTIC ACTIVITY IN THE ZIRCONOCENE - ALUMOXANE POLYMERIZATION OF ETHYLENE [J].
HARLAN, CJ ;
BOTT, SG ;
BARRON, AR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (24) :6465-6474
[8]   STUDIES ON RARE-EARTH ALLYL COMPOUNDS .4. THE CRYSTAL-STRUCTURE OF [LI2(MU-C3H5)(C4H8O2)3][CE(ETA-3-C3H5)4] [J].
HUANG, ZE ;
CHEN, MQ ;
QIU, WJ ;
WU, WL .
INORGANICA CHIMICA ACTA, 1987, 139 (1-2) :203-207
[9]  
LEHMKUHL H, 1970, METHODEN ORG, V13, P127
[10]  
MAIWALD S, 1997, IN PRESS MACROMOLECU