J. Okuda et al., SYNTHESIS AND CHARACTERIZATION OF TITANIUM COMPLEXES CONTAINING THE 1-(3-BUTENYL)-2,3,4,5-TETRAMETHYLCYCLOPENTADIENYL LIGAND, Journal of organometallic chemistry, 495(1-2), 1995, pp. 195-202
A series of titanium complexes containing the 1-(3-butenyl)-2,3,4,5-te
tramethylcyclopentadienyl ligand C(5)Me(4)CH(2)CH(2)CH=CH2 (Cp(=)) hav
e been synthesized and characterized. The dichloro complex Cp(2)(=)TiC
l(2) was prepared by the reaction of LiCp(=) and TiCl3 in dimethoxyeth
ane, followed by oxidation using lead dichloride. Cp(2)(=)TiCl(2) was
converted into the dimethyl derivative Cp(2)(=)TiMe(2), the molecular
structure of which was confirmed by an X-ray structural analysis, whic
h showed it to be a peralkyl titanocene complex containing the two pen
dent 3-butenyl side chains in the lateral positions of the bent metall
ocene unit. The reaction of Cp(2)(=)TiMe(2) with B(C6F5)(3) was monito
red by NMR spectroscopy. Cp(=)TiCl(3), which was used to synthesize Cp
(=)CpTiCl(2) by reacting with LiCp, was prepared from the reaction bet
ween Cp(=)SiMe(3) and TiCl4. Cp(=)CpTiCl(2) was further converted into
Cp(=)CpTiMe(2) and Cp(=)CpTi(OTf)(2). A significantly improved method
for the preparation of 1-(3-butenyl)-2,3,4,5-tetramethylcyclopentadie
ne was developed.