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 beta -and gamma-agostic isomers. In addition, while free rotation of the beta-methyl group results in a single, averaged gamma-H atom resonance at higher temperatures, decoalescence occurs below similar to 200 K, and the resonance of the gamma-agostic hydrogen atom at delta similar to -7.4 is observed. Reaction of [Cp2Ti(CD3)(CD2Cl2)](+) with TMVS results in the formation of [Cp2TiCH2CH(CD3)(SiMe3)](+), which converts, via reversible beta-elimination, to an equilibrium mixture of specifically [Cp2TiCH2CH(CD3)(SiMe3)](+) and [Cp2TiCD2CD(CH3)(SiMe3)](+). Complementing this conventional process, exchange spectroscopy experiments show that the beta-H atom of [Cp2TiCH2CHMe(SiMe3)](+) undergoes exchange with the three hydrogen atoms of the beta-methyl group (beta-H/gamma-H exchange) but not with the two alpha-H atoms. This exchange process is completely shut down when [Cp2TiCH2CH(CD3)(SiMe3)](+) is used, suggesting an HID kinetic isotope effect much larger (apparently >16 000) than the maximum possible for an over-the-barrier process. It is proposed that beta-H/gamma-H exchange is facilitated by quantum mechanical proton tunnelling in which a hydrogen atom of the 2-methyl group of the alkene-hydride deinsertion product [Cp2TiH{CH2=CMe(SiMe3)}](+) undergoes reversible exchange with the hydride ligand via the allyl dihydrogen species [Cp2TiH2{(eta(3)-CH2C(SiMe3)CH2}](+). Complementing these findings, DFT calculations were carried out to obtain energies and NMR parameters for all relevant species and thence to obtain better insight into the agostic preference(s) of complex III and the observed exchange processes. In all cases where comparisons between experimental and calculated data were possible, agreement was excellent.