Mechanistic aspects of chemo- and regioselectivity in Cp2ZrCl2 – catalyzed alkene cycloalumination by AlEt3
Mechanistic aspects of chemo- and regioselectivity in Cp2ZrCl2 – catalyzed alkene cycloalumination by AlEt3
The reactions of styrene and 1-hexene with zirconacyclopropane and the bimetallic five-membered Zr,Al-complex [Cp2Zr(m-Cl)CH2CH2AlEt2] as catalytically active sites in Cp2ZrCl2-catalyzed cyclo- alumination of a-olefins with AlEt3 have been studied by DFT quantum chemical methods (PBE/3z, B3LYP/VDZ, B3LYP(GD3)/VDZ, M06-2X/VDZ, M06-2X/VTZ//VDZ). It was shown that key intermediates can exist in dynamic equilibrium with each other, and with ClAlEt2 adducts. 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 regio- selectivity on the substrate structure and the minor by-products formation. The applicability of M06-2X/ cc-pVTZ-PP//M06-2X/cc-pVDZ-PP and PBE/3z methods for the description of the available experimental data was shown.
135-143
Tyumkina, Tatyana V.
4af5b88b-f27d-4207-96a6-cc4e021346d1
Islamov, Denis N.
f854fadc-0c2b-4e3d-ba2f-ed5f7e39ed1f
Parfenova, Lyudmila V.
22382afc-4fee-45fc-b0e2-feeb5a1a9b62
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Khalilov, Leonard M.
48fd99b3-f32b-4a3d-b170-055874e47168
Dzhemilev, Usein M.
87786dc0-61b3-4f8b-80b3-ca85e8c25c9e
1 November 2016
Tyumkina, Tatyana V.
4af5b88b-f27d-4207-96a6-cc4e021346d1
Islamov, Denis N.
f854fadc-0c2b-4e3d-ba2f-ed5f7e39ed1f
Parfenova, Lyudmila V.
22382afc-4fee-45fc-b0e2-feeb5a1a9b62
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Khalilov, Leonard M.
48fd99b3-f32b-4a3d-b170-055874e47168
Dzhemilev, Usein M.
87786dc0-61b3-4f8b-80b3-ca85e8c25c9e
Tyumkina, Tatyana V., Islamov, Denis N., Parfenova, Lyudmila V., Whitby, Richard J., Khalilov, Leonard M. and Dzhemilev, Usein M.
(2016)
Mechanistic aspects of chemo- and regioselectivity in Cp2ZrCl2 – catalyzed alkene cycloalumination by AlEt3.
Journal of Organometallic Chemistry, 822, .
(doi:10.1016/j.jorganchem.2016.08.019).
Abstract
The reactions of styrene and 1-hexene with zirconacyclopropane and the bimetallic five-membered Zr,Al-complex [Cp2Zr(m-Cl)CH2CH2AlEt2] as catalytically active sites in Cp2ZrCl2-catalyzed cyclo- alumination of a-olefins with AlEt3 have been studied by DFT quantum chemical methods (PBE/3z, B3LYP/VDZ, B3LYP(GD3)/VDZ, M06-2X/VDZ, M06-2X/VTZ//VDZ). It was shown that key intermediates can exist in dynamic equilibrium with each other, and with ClAlEt2 adducts. 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 regio- selectivity on the substrate structure and the minor by-products formation. The applicability of M06-2X/ cc-pVTZ-PP//M06-2X/cc-pVDZ-PP and PBE/3z methods for the description of the available experimental data was shown.
Text
JOMC_paper_final authors_submitted.pdf
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Submitted date: 10 March 2016
Accepted/In Press date: 20 August 2016
e-pub ahead of print date: 26 August 2016
Published date: 1 November 2016
Organisations:
Organic Chemistry: Synthesis, Catalysis and Flow
Identifiers
Local EPrints ID: 399886
URI: http://eprints.soton.ac.uk/id/eprint/399886
ISSN: 0022-328X
PURE UUID: e4af2aca-8d16-45a4-8328-10a2886395ff
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Date deposited: 02 Sep 2016 10:15
Last modified: 15 Mar 2024 05:51
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Contributors
Author:
Tatyana V. Tyumkina
Author:
Denis N. Islamov
Author:
Lyudmila V. Parfenova
Author:
Leonard M. Khalilov
Author:
Usein M. Dzhemilev
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