کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1323052 | 1499919 | 2012 | 7 صفحه PDF | دانلود رایگان |
Transmetallation leading to formation of n-Pr–Al bond in the Cp2Zr(n-Pr)Cl–XAlBui2 (X = H, Cl, Bui) couple was studied using PBEPBE/3ζ and RI-MP2/Λ2//PBEPBE/3ζ approaches. Calculation results were corrected by taking into account of nonspecific solvent effect (toluene). Depending on the nature of organoaluminum compound, either decomposition of alkylalane self-associates (HAlBui2 and ClAlBui2 cases) or alkyl group transfer reaction from Zr to Al atom (AlBui3 case) could be a rate-determining step of the process. The modeling of kinetics with calculated Gibbs free energies for elementary steps of the process shows that transmetallation rates decrease in the following order: ClAlBui2 > HAlBui2 >> AlBui3.
Transmetallation Mechanism in the Cp2ZrPrnCl–XAlBui2 (X = H, Cl, Bui) system. Figure optionsDownload as PowerPoint slideHighlights
► Transmetallation in the Cp2ZrPrnCl–XAlBui2 (X = H, Cl, Bui) system was studied.
► Rate-determining step depends on the nature of organoaluminum compound.
► Transmetallation rates decrease in the order: ClAlBui2 > HAlBui2 >> AlBui3.
Journal: Journal of Organometallic Chemistry - Volume 718, 1 November 2012, Pages 117–123