[Cp2TiCH2CHMe(SiMe3)]+, an Alkyl–Titanium Complex Which (a) Exists in Equilibrium between a β‑Agostic and a Lower Energy γ‑Agostic Isomer and (b) Undergoes Hydrogen Atom Exchange between α‑, β‑, and γ‑Sites via a Combination of Conventional β‑Hydrogen Elimination–Reinsertion and a Nonconventional CH Bond Activation Process Which Involves Proton Tunnelling

[Cp2TiCH2CHMe(SiMe3)]+, an Alkyl–Titanium Complex Which (a) Exists in Equilibrium between a β‑Agostic and a Lower Energy γ‑Agostic Isomer and (b) Undergoes Hydrogen Atom Exchange between α‑, β‑, and γ‑Sites via a Combination of Conventional β‑Hydrogen Elimination–Reinsertion and a Nonconventional CH Bond Activation Process Which Involves Proton Tunnelling

The compound [Cp2Ti(Me)(CD2Cl2)][B(C6F5)4] reacts with trimethylvinylsilane (TMVS) to form the 1,2-insertion product [Cp2TiCH2CHMe(SiMe3)]+ (III), which exists in solution as equilibrating β- and γ-agostic isomers. In addition, while free rotation of the β-methyl group results in a single, averaged...

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Veröffentlicht in:Journal of the American Chemical Society 2013-11, Vol.135 (46), p.17514-17527
Hauptverfasser: Dunlop-Brière, Alexandre F, Baird, Michael C, Budzelaar, Peter H. M
Format: Artikel
Sprache:eng
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