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- W1991301071 abstract "The β-allyl zirconacyclobutane complex Cp*2Zr[CH2CH(CH2CHCH2)CH2] (7) reacted rapidly with B(C6F5)3 in CD2Cl2 at −78 °C to form the zwitterionic d0 zirconium(IV) chelate complex Cp*2Zr[η1,η2-CH2CH[CH2B(C6F5)3]CH2CHCH2] (2a and 2b). Low-temperature 1H, 13C, TOCSY1D, and NOESY1D NMR spectroscopy of 2 established the bonding of the tethered alkene to the d0 metal center. A dynamic NMR study of the interconversion of 2a and 2b allowed measurement of the alkene dissociation energy (ΔG⧧ = 10.5 (2a to 2b) and 10.3 (2b to 2a) kcal mol-1), but the complex decomposed before the barrier for site epimerization at the zirconium center could be determined. Reaction of 7 with [(C6H5)2(CH3)NH][B(C6F5)4] led to the formation of two isomeric d0 zirconium(IV)−alkyl−alkene chelates Cp*2Zr[η1,η2-CH2CH(CH3)CH2CHCH2][B(C6F5)4] (8a and 8b). This more thermally stable zirconium−alkyl−alkene complex allowed the measurement of barriers associated with decomplexation of the alkene (ΔG⧧ =10.7 and 11.1 kcal mol-1) and site epimerization at the zirconium center (ΔG⧧ =14.4 kcal mol-1) by line shape analysis of variable-temperature 1H and 13C NMR spectra." @default.
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- W1991301071 date "2000-08-19" @default.
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- W1991301071 title "Measurement of Barriers for Alkene Dissociation and for Inversion at Zirconium in a d<sup>0</sup> Zirconium−Alkyl−Alkene Complex" @default.
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