Collect. Czech. Chem. Commun.
2008, 73, 967-982
https://doi.org/10.1135/cccc20080967
Reactions of Doubly Tucked-In Permethyltitanocene with tert-Butanol and Propargyl Alcohol. The Crystal Structures of Unusual Hydrolytic Byproducts
Jiří Pinkasa, Róbert Gyepesb, Ivana Císařováb, Petr Štěpničkab, Michal Horáčeka, Jiří Kubištaa, Vojtech Vargac and Karel Macha,*
a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 182 23 Prague 8, Czech Republic
b Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
c Research Institute of Inorganic Chemistry, a.s., Revoluční 84, 400 01 Ústí nad Labem, Czech Republic
Abstract
Reactions of double tucked-in permethyltitanocene [Ti{η3:η4-C5Me3(CH2)2}(η5-C5Me5)] (1) with tert-butanol or propargyl alcohol in toluene proceeded sluggishly even with excess of the alcohol and at elevated temperature. The alcoholysis of 1 with tert-butanol afforded [Ti(η5-C5Me5)(Ot-Bu)3] (3) as the major product and Ti(Ot-Bu)4 as the minor one. The other product of the alcoholysis was pentamethylcyclopentadiene. The only isolated crystalline product was the very minor hydrolytic byproduct [{TiIII(η5-C5Me5)2}(μ-O){TiIV(Ot-Bu)3}] (2). The alcoholysis of 1 containing traces of LiI with HOCH2C≡CH, containing apparently more water than t-BuOH, gave an inseparable mixture of oily products from which several crystals of an unintended hydrolytic byproduct [{Ti(η5-C5Me5)(OCH2C≡CH)(μ-O)}3LiI] (4) were isolated. X-ray crystal structures of 2 and 4 were determined.
Keywords: Titanium; Double tucked-in titanocene; Allyl-diene ligand; Alcoholysis; tert-Butanol; Propargyl alcohol; NMR spectra; Hydrolysis byproduct; Crystal structures.
References: 36 live references.
