Dialkyl titanium complexes that contain a sulfur-linked bis(phenolato) ligand: The structure of an olefin polymerization catalyst precursor

被引:27
作者
Fokken, S [1 ]
Reichwald, F [1 ]
Spaniol, TP [1 ]
Okuda, J [1 ]
机构
[1] Univ Mainz, Inst Anorgan Chem & Analyt Chem, D-55099 Mainz, Germany
关键词
titanium; phenolato ligands; alkyl complexes; polymerization catalysts;
D O I
10.1016/S0022-328X(02)01802-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The sulfur-linked bis(phenol) 2,2'-thiobis(2-tert-butyl-4-methylphenol), tbmpH(2), reacted cleanly with titanium tetrachloride to give the orange titanium dichloro complex [Ti(tbmp)Cl-2](2) in virtually quantitative yield. Reaction of the dichloro, complex [Ti(tbmp)Cl-2](2) with methyllithium. at low temperature gave the unexpectedly thermally robust, yellow dimethyl complex [Ti(tbmp)Me-2]. The reaction of the dichloro complex with benzyl Grignard reagent in pentane afforded the highly crystalline dibenzyl complex [Ti(tbmp)(CH2Ph)(2)] as a 1,4-dioxane adduct. The single crystal X-ray crystallography revealed a centrosymmetric 1,4-dioxane-bridged molecule that contains two fragments containing six-coordinate titanium centers with the tridentate tbmp ligand in a facial fashion and two eta(1)-benzyl ligands. When [Ti(tbmp)Me-2] was activated with B(C6F5)(3) in toluene, ethylene was polymerized. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:158 / 163
页数:6
相关论文
共 26 条
[11]   Theoretical studies of ethylene polymerization reactions catalyzed by zirconium and titanium chelating alkoxide complexes [J].
Froese, RDJ ;
Musaev, DG ;
Matsubara, T ;
Morokuma, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (31) :7190-7196
[12]   Theoretical studies of the factors controlling insertion barriers for olefin polymerization by the titanium-chelating bridged catalysts. A search for more active new catalysts [J].
Froese, RDJ ;
Musaev, DG ;
Morokuma, K .
ORGANOMETALLICS, 1999, 18 (03) :373-379
[13]   TI COMPLEX CATALYSTS INCLUDING THIOBISPHENOXY GROUP AS A LIGAND FOR OLEFIN POLYMERIZATION [J].
MIYATAKE, T ;
MIZUNUMA, K ;
KAKUGO, M .
MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA, 1993, 66 :203-214
[14]  
MIYATAKE T, 1989, MAKROMOL CHEM-RAPID, V10, P349
[15]   Titanium complexes having chelating diaryloxo ligands bridged by tellurium and their catalytic behavior in the polymerization of ethylene [J].
Nakayama, Y ;
Watanabe, K ;
Ueyama, N ;
Nakamura, A ;
Harada, A ;
Okuda, J .
ORGANOMETALLICS, 2000, 19 (13) :2498-2503
[16]   Syndiospecific polymerization of styrene using methylaluminoxane-activated bis(phenolato)titanium complexes [J].
Okuda, J ;
Masoud, E .
MACROMOLECULAR CHEMISTRY AND PHYSICS, 1998, 199 (04) :543-545
[17]   SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR TITANIUM COMPLEXES CONTAINING A BIS(PHENOXY) LIGAND DERIVED FROM 2,2'-METHYLENE-BIS(6-TERT-BUTYL-4-METHYLPHENOL) [J].
OKUDA, J ;
FOKKEN, S ;
KANG, HC ;
MASSA, W .
CHEMISCHE BERICHTE, 1995, 128 (03) :221-227
[18]   Synthesis and structural characterization of titanium complexes containing a sulfinyl-bridged bis(phenolato) ligand [J].
Okuda, J ;
Fokken, S ;
Kang, HC ;
Massa, W .
POLYHEDRON, 1998, 17 (5-6) :943-946
[19]   Molecular structure of 2,2'-thiobis(4-methyl-6-tert-butylphenoxy) titanium diisopropoxy. Influence of titanium-sulfur interaction on coordination geometry [J].
Porri, L ;
Ripa, A ;
Colombo, P ;
Miano, E ;
Capelli, S ;
Meille, SV .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 514 (1-2) :213-217
[20]   PENTACOORDINATED MOLECULES .95. INFLUENCE OF PHOSPHORUS SULPHUR BONDING IN THE FORMATION OF OCTAHEDRALLY COORDINATED CYCLIC PENTAOXYPHOSPHORANES [J].
PRAKASHA, TK ;
DAY, RO ;
HOLMES, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (07) :2690-2695