Reactions of Doubly Tucked-In Permethyltitanocene with tert-Butanol and Propargyl Alcohol. The Crystal Structures of Unusual Hydrolytic Byproducts
Abstract
Reactions of double tucked-in permethyltitanocene [Ti{η3:η4-C5Me3(CH2)2}(η5-C5Me5)] (1) with t-butanol or propargyl alcohol in toluene proceeded sluggishly even with excess of the alcohol and at elevated temperature. The alcoholysis of 1 with t-butanol afforded [Ti(η5-C5Me5)(Ot-Bu)3] (3) as the major product and Ti(OtBu)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.