The mechanism of η(η5:η5-fulvalene)-di-μ-chloro-bis (η5-cyclopentadienyltitanium) formation in the system Cp2TiCl2 : LiAlH4 : Olefinic solvent |
| |
Authors: | Karel Mach Helena Antropiusová Vladimiŕ Hanuš Alena Dosedlová |
| |
Institution: | (1) J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, Máchova 7, 12138 Prague 2, Czechoslovakia |
| |
Abstract: | Summary The reduction of Cp2TiCl2 with LiAlH4 in olefinic solvents at temperatures above 100° leads to the formation of µ-(
5 :
5-fulvalene)-di-µ-chloro-bis(
5-cyclopentadienyl-titanium) (1) and finally to µ-(
5 :
15-fulvalene)-di-µ-hydrido-bis (
5-cyclopentadienyltitanium). The first step of the reduction includes mainly the formation of the dimer of bis(
5-cyclopentadienyl)titanium(III) chloride, (Cp2TiCl)2. The mechanism of its conversion into (1) involves the formation of an intermediate bis(
5-cyclopentadienyl)titanium(III) hydride species which reacts immediately with the olefinic solvent to give bis(
5-cyclopentadienyl)alkyltitanium(III) compounds. The formation of the fulvalene ligand in (1) is explained by the interaction of the alkyltitanium compound with the cyclopentadienyl ligands of (Cp2TiCl)2 resulting in hydrogen transfer to the olefinic solvent. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |