RT info:eu-repo/semantics/article
T1 Allylsilylcyclopentadienyl Group 4 metal complexes: synthesis, structure and reactivity
A1 Cano Sierra, Jesús
A1 Gómez Sal, Pilar
A1 Heinz, Georg
A1 Martínez Martínez, Gema
A1 Royo Gracia, Pascual
K1 Metallocene
K1 Titanium
K1 Zirconium
K1 Polymerization
K1 Cationic species
K1 Ciencia
K1 Química inorgánica
K1 Science
K1 Chemistry, inorganic
AB (Allyldimethyl)silyl-substituted cyclopentadiene C5H5SiMe2(CH2CH /CH2) (1) and indene C9H7 /1-SiMe2(CH2CH /CH2) (2)were synthesized by reaction of SiMe2(CH2CH /CH2)Cl with NaC5H5 or LiC9H7, respectively. Metallation of 1 with n-BuLi andTlOEt gave the corresponding lithium 3 and thallium 5 salts. The disilylcylopentadienes C5H4 /1-SiMe3 /1-SiMe2(CH2CH /CH2) (6)and C5H4 /1,1-[SiMe2(CH2CH /CH2)]2 (7) were prepared by reaction of 3 with the corresponding chlorosilanes. Compound 7reacted with TiCl4 to give the monocyclopentadienyl compound [Ti{h5-C5H4SiMe2(CH2CH /CH2)}Cl3] (8), while 5 was used toprepare the titanocenes [Ti(h5-Cp){h5-C5H4SiMe2(CH2CH /CH2)}Cl2] (Cp /C5H4SiMe2(CH2CH /CH2) 9, C5H5 10, C5Me5 11) byreaction with the appropriate TiCpCl3 derivative. The related dicyclopentadienyl [Zr{h5-C5H4SiMe2(CH2CH /CH2)}2Cl2] (12),[Zr(h5-C5H5){h5-C5H4SiMe2(CH2CH /CH2)}Cl2] (13), and indenyl [Zr(h5-C5H5){h5-C9H6SiMe2(CH2CH /CH2)}Cl2] (14) zirconiumderivatives were isolated by reaction of ZrCl4 and Zr(h5-C5H5)Cl3  /DME with the lithium salts 3 and 4, respectively.Alkylation of the metallocene complexes using MeLi, MgMeCl, Mg(CH2Ph)Cl and Mg(CH2Ph)2(THF)2 afforded the monomethyltitanium [Ti(h5-C5H5){h5-C5H4SiMe2(CH2CH /CH2)}ClMe] (15) and the dialkyl cyclopentadienyl [M(h5-C5H5){h5-C5H4SiMe2(CH2CH /CH2)}R2] (R /Me, M /Ti 16, Zr 18; R /CH2Ph, M /Ti 20, Zr 22), [Zr{h5-C5H4SiMe2(CH2CH /CH2)}2R2] (R /Me17, CH2Ph 21) and indenyl derivatives [Zr(h5-C5H5){h5-C9H6SiMe2(CH2CH /CH2)}R2] (R /Me 19, CH2Ph 23). The molecularstructure of 11 was studied by X-ray diffraction methods. The reactions of the dialkyl derivatives with B(C6F5)3 were monitored byNMR spectroscopy at variable temperature. The catalytic activity of the dichloro zirconium complexes in the presence ofmethylalumoxane (MAO) for ethylene polymerization was determined.
PB Elsevier
SN 0020-1693
YR 2003
FD 2003
LK http://hdl.handle.net/10017/4196
UL http://hdl.handle.net/10017/4196
LA eng
NO Financial support of our work by MCyT (ProjectMAT2001-1309) is gratefully acknowledged. G.H., G.Mand J.C are grateful to to the Alexander von HumboldtStiftung,MEC and CAM for fellowships.
DS MINDS@UW
RD 24-abr-2024