2016
DOI: 10.1016/j.jorganchem.2016.08.019
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Mechanistic aspects of chemo- and regioselectivity in Cp2ZrCl2-catalyzed alkene cycloalumination by AlEt3

Abstract: The reactions of styrene and 1-hexene with zirconacyclopropane and the bimetallic five-membered Comparative analysis was carried out for the energy characteristics of alternative pathways in the reaction of styrene or 1-hexene with the intermediates, implying different orientations of the substrates towards the Zr-C bond. The obtained data were used to elucidate the reasons for the observed dependence of the reaction regioselectivity on the substrate structure and the minor by-products formation. The applicabi… Show more

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Cited by 11 publications
(12 citation statements)
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References 66 publications
(26 reference statements)
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“…Relatively stable di-Zr complexes [18] could hardly be seen as prototype of catalytic species. Zr-Al complexes can vary in a number of coordinated Al atoms [15,19,20,21,22,23,24,25,26,27]. To explain experimental facts, we recently proposed a binuclear Zr-Al model (Scheme 2) [13,28] involving the catalytic species that are closely related to discrete ionic pairs containing Zr-(μ-Me) 2 AlMe 2 fragments formed at the initial stage of zirconocene dichloride activation by MAO [29,30,31,32,33,34,35].…”
Section: Introductionmentioning
confidence: 99%
“…Relatively stable di-Zr complexes [18] could hardly be seen as prototype of catalytic species. Zr-Al complexes can vary in a number of coordinated Al atoms [15,19,20,21,22,23,24,25,26,27]. To explain experimental facts, we recently proposed a binuclear Zr-Al model (Scheme 2) [13,28] involving the catalytic species that are closely related to discrete ionic pairs containing Zr-(μ-Me) 2 AlMe 2 fragments formed at the initial stage of zirconocene dichloride activation by MAO [29,30,31,32,33,34,35].…”
Section: Introductionmentioning
confidence: 99%
“…Previously, we have studied the mechanism of the reaction of complex 2 with styrene and 1-hexene . We have found that the insertion of the olefin molecule into the complex is accompanied by displacement of the ClAlEt 2 molecule with zirconacyclopropane 5 formation.…”
Section: Resultsmentioning
confidence: 99%
“…Thus, we carried out a theoretical study of the above-mentioned steps of catalytic cycloalumination at the DFT level using the PBE/3ζ and M06-2X/cc-pVDZ quantum chemical methods and comparative analysis of the possible reaction pathways with identification of the most probable ones. This method has been shown to be quite reliable for investigation of the organometallic systems and is recommended for calculations of Zr-mediated reactions. ,, …”
Section: Introductionmentioning
confidence: 99%
“…The nature of the interaction of metallocene complexes of zirconium and organoaluminum compounds has been studied in detail and continues to be studied by L.V. Parfenova with co-workers [4,5]. However, there are no literature data on the study of the exchange reactions of zirconocene complexes with organocin reagents.…”
Section: Introductionmentioning
confidence: 99%