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Synthesis and reactivity of new mixed dicyclopentadienyl Group 4 metal complexes with the doubly bridged bis(dimethylsilanediyl)-cyclopentadiene-(η5-cyclopentadienyl) ligand

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Authors
Gómez García, RobertoUniversity of Alcalá Author; Royo Gracia, PascualUniversity of Alcalá Author
Identifiers
Permanent link (URI): http://hdl.handle.net/10017/4237
DOI: 10.1016/S0022-328X(99)00111-4
ISSN: 0022-328X
Publisher
Elsevier
Date
1999
Affiliation
Universidad de Alcalá. Departamento de Química Inorgánica
Bibliographic citation
Journal of Organometallic Chemistry, 1999, v.583, n.1-2, p.86-93
Keywords
Titanium
Zirconium
Hafnium
Dicyclopentadienyl complexes
Polyethylene
Project
PB97-0776 (Ministerio de Educación y Cultura)
I+D0033/94 (Comunidad de Madrid)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1016/S0022-328X(99)00111-4
Rights
© Elsevier, 1999
Access rights
info:eu-repo/semantics/openAccess
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Abstract
The monocyclopentadienyl titanium complex [Ti{(C5H4)(SiMe2)2(η5-C5H3)} Cl3] 3 and the dichloro mixed dicyclopentadienyl Group 4 metal complexes [M(η5-C5R5){(C5H4)(SiMe2)2(η5-C5H3)} Cl2] (R=H; M=Ti 4, Zr 5, Hf 6; R=Me; M=Ti 7) containing the doubly bridged bis(dimethylsilanediyl)-cyclopentadiene-(η5-cyclopentadienyl) ligand were prepared in high yields by reaction of the monolithium salt Li[(C5H4)(SiMe2)2(C5H3)] 2 with equimolar amounts of TiCl4 or the monocyclopentadienyl complexes [Cp′MCl3], respectively. Reactions of the chloro complexes with various alkylating agents afforded the chloroalkyl [M(η5-C5H5){(C5H4)(SiMe2)2(η5-C5H3)}ClR] (M=Ti; R=Me 8, Et 9; M=Zr, R=Me 10, Et 11, CH2Ph 12; M=Hf, R=CH2Ph 13) and dialkyl [M(η5-C5R5){(C5H4)(SiMe2)2(η5-C5H3)}Me2] (M=Ti; R=H 14, Me 15; M=Zr; R=H 16, compounds. Formation of the heterodinuclear complex [Zr(η5-C5H5)Cl2(η5-C5H3)(SiMe2)2(η5-C5H3)Ti(NMe2)3] 17 with amine elimination was observed by 1H-NMR spectroscopy when complex 5 was reacted with Ti(NMe2)4. The catalytic activity of compounds 3–5 for ethylene polymerization has been studied using MAO as cocatalyst.
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