title: Dihydrogen and silane addition to base-free, monomeric bis(cyclopentadienyl)titanium oxides.
abstract: Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (eta5-C5Me4R)2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (eta5-C5Me4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23 degrees C, yielding the titanocene hydroxy hydride complexes (eta5-C5Me4R)2Ti(OH)H. For (eta5-C5Me4SiMe3)2Ti=O, the kinetics of hydrogenation were first-order in dihydrogen and exhibited a normal, primary kinetic isotope effect of 2.7(3) at 23 degrees C consistent with a 1,2-addition pathway. Isotope effects of the same direction but smaller magnitudes were determined for silane addition.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Tamara E
authors.initials: TE
authors.lastname: Hanna
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik