Collect. Czech. Chem. Commun.
2005, 70, 1589-1603
https://doi.org/10.1135/cccc20051589
Preparation and Crystal Structure of Bis(tert-butyltetramethylcyclopentadienyl)dichlorotitanium
Lenka Lukešováa, Róbert Gyepesb, Jiří Pinkasa, Michal Horáčeka, Jiří Kubištaa, Jiří Čejkaa and Karel Macha,*
a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic
b Department of Inorganic Chemistry, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
Abstract
[TiCl2(η5-C5Me4t-Bu)2] (1) was prepared by the reaction of [TiCl3(thf)3] with 2 equivalents of Li(η5-C5Me4t-Bu) (made by adding BuLi to a 1.33 molar excess of a mixture of tert-butyltetramethylcyclopentadiene isomers in THF) and subsequent oxidation of the Ti(III) intermediate to 1 by adding aqueous HCl. Neglecting the presence of cyclopentadiene isomers not forming the cyclopentadienide anion in the isomer mixture used for the synthesis of 1 resulted in the formation of hydrolytic product [{TiCl2(η5-C5Me4t-Bu)}2(μ-O)] (2) and a considerable decrease of yield of 1. The half sandwich complex [TiCl3(η5-C5Me4t-Bu)] (3) was obtained by synproportionation of 1 and TiCl4. Crystal structures of 1, 2, and 3 were determined. The electronic absorption spectra of 1 and 3 indicate a stronger electron-donor effect of tert-butyl group compared with methyl group.
Keywords: Titanium; Titanocene dichloride; tert-Butyltetramethylcyclopentadiene; Half-sandwich complexes; Metallocenes; Cyclopentadienes; tert-Butyl group; Electronic effect; Hydrolysis products; Crystal structures.
References: 47 live references.
