Abstract
New cyclopentadiene preligands and monocyclopentadienyltitanium compounds bearing a vinyl and one or two chloro groups on the silyl substituent of the Cp ring have been prepared with the aim of incorporating a reactive anchoring group into the cyclopentadienylsilyl functionality. Reaction of the new titanium monocyclopentadienyl complexes, [Ti{η5-C5H4Si(CH=CH2)XCl}Cl3] (X = Me, 2a; Cl, 2b), with an equimolar amount of iBu7Si7O9(OH)3 (5) affords either the kinetic control products, namely the corresponding corner-capped cyclopentadienyl derivatives [Ti{η5-C5H4Si(CH=CH2)XCl}(iBu7Si7O12-κ3O3)] (X = Me, 6a; Cl, 6b), or the thermodynamic ones, namely the cyclopentadienyl-silsesquioxane complexes [Ti{η5-C5H4Si(CH=CH2)XOiBu7Si7O11-κ2O2}Cl] (X = Me, 7a; Cl, 7b), depending on the reaction conditions. This transformation is not selective for 7b since it rapidly isomerizes, via a second exchange between a Ti-O(POSS) (POSS = polyhedral oligomeric silsesquioxane) bond and a CpSi-Cl bond, to give the final doubly connected cyclopentadienyl-silsesquioxane compound [Ti{η5-C5H4Si(CH=CH2)O2iBu7Si7O10-κO)Cl] (8).
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