Preparation and Crystal Structure of Bis(tert-butyltetramethylcyclopentadienyl)dichlorotitanium

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Title:Preparation and Crystal Structure of Bis(tert-butyltetramethylcyclopentadienyl)dichlorotitanium
Creators:
Lukešová, Lenka
Gyepes, Róbert
Pinkas, Jiří
Horáček, Michal
Kubišta, Jiří
Čejka, Jiří
Mach, Karel
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 70, 10, pp. 1589-1603
Uncontrolled Keywords:Titanocene dichloride, Titanium, Hydrolysis products, <i>tert</i>-Butyltetramethylcyclopentadiene, Electronic effect, <i>tert</i>-Butyl group, Cyclopentadienes, Crystal structures, Metallocenes, Half-sandwich complexes

Abstract

[TiCl<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub><i>t</i>-Bu)<sub>2</sub>] (<strong>1</strong>) was prepared by the reaction of [TiCl<sub>3</sub>(thf)<sub>3</sub>] with 2 equivalents of Li(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub><i>t</i>-Bu) (made by adding BuLi to a 1.33 molar excess of a mixture of <i>tert</i>-butyltetramethylcyclopentadiene isomers in THF) and subsequent oxidation of the Ti(III) intermediate to <strong>1</strong> by adding aqueous HCl. Neglecting the presence of cyclopentadiene isomers not forming the cyclopentadienide anion in the isomer mixture used for the synthesis of <strong>1</strong> resulted in the formation of hydrolytic product [{TiCl<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub><i>t</i>-Bu)}<sub>2</sub>(μ-O)] (<strong>2</strong>) and a considerable decrease of yield of <strong>1</strong>. The half sandwich complex [TiCl<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub><i>t</i>-Bu)] (<strong>3</strong>) was obtained by synproportionation of <strong>1</strong> and TiCl<sub>4</sub>. Crystal structures of <strong>1</strong>, <strong>2</strong>, and <strong>3</strong> were determined. The electronic absorption spectra of <strong>1</strong> and <strong>3</strong> indicate a stronger electron-donor effect of <i>tert</i>-butyl group compared with methyl group. <p>

Title:Preparation and Crystal Structure of Bis(tert-butyltetramethylcyclopentadienyl)dichlorotitanium
Creators:
Lukešová, Lenka
Gyepes, Róbert
Pinkas, Jiří
Horáček, Michal
Kubišta, Jiří
Čejka, Jiří
Mach, Karel
Uncontrolled Keywords:Titanocene dichloride, Titanium, Hydrolysis products, <i>tert</i>-Butyltetramethylcyclopentadiene, Electronic effect, <i>tert</i>-Butyl group, Cyclopentadienes, Crystal structures, Metallocenes, Half-sandwich complexes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:70
Number:10
Page Range:pp. 1589-1603
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20051589UNSPECIFIED
ID Code:2427
Item Type:Article
Deposited On:06 Feb 2009 17:18
Last Modified:06 Feb 2009 16:18

Citation

Lukešová, Lenka; Gyepes, Róbert; Pinkas, Jiří; Horáček, Michal; Kubišta, Jiří; Čejka, Jiří; Mach, Karel (2005) Preparation and Crystal Structure of Bis(tert-butyltetramethylcyclopentadienyl)dichlorotitanium. Collection of Czechoslovak Chemical Communications, 70 (10). pp. 1589-1603. ISSN 0010-0765

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