Open Access

Molecules

, volume 24 , issue 19 , pages 3565

Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism

Ilya E. Nifant'ev ^{1, 2}

Alexander Vinogradov ¹

Alexey Vinogradov ¹

Stanislav Karchevsky ³

Pavel Ivchenko ^{1, 2}

Hide authors affiliations Show authors affiliations: 3 affiliations

A.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, Russia |

Chemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str., Building 3, 119991 Moscow, Russia |

Joint-Stock Company “Institute of Petroleum Refining and Petrochemistry”, 12 Iniciativnaya Str., Ufa, 450065 Republic of Bashkortostan, Russia |

Publication type: Journal Article

Publication date: 2019-10-02

MDPI

Molecules

scimago Q1

wos Q2

SJR: 0.865

CiteScore: 8.6

Impact factor: 4.6

ISSN: 14203049

DOI: 10.3390/molecules24193565

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PubMed ID: 31581621

Organic Chemistry

Drug Discovery

Physical and Theoretical Chemistry

Pharmaceutical Science

Molecular Medicine

Analytical Chemistry

Chemistry (miscellaneous)

Abstract

Zirconocene-mediated selective dimerization of α-olefins usually occurs when precatalyst (η5-C5H5)2ZrCl2 is activated by minimal excess of methylalumoxane (MAO). In this paper, we present the results of density functional theory (DFT) simulation of the initiation, propagation, and termination stages of dimerization and oligomerization of propylene within the framework of Zr-Al binuclear mechanism at M-06x/DGDZVP level of theory. The results of the analysis of the reaction profiles allow to explain experimental facts such as oligomerization of α-olefins at high MAO/(η5-C5H5)2ZrCl2 ratios and increase of the selectivity of dimerization in the presence of R2AlCl. The results of DFT simulations confirm the crucial role of the presence of chloride in the selectivity of dimerization. The molecular hydrogen was found in silico and proven experimentally as an effective agent that increases the rate and selectivity of dimerization.

Found

6 citations

Parfenova Lyudmila

🥼 🤝

DSc in Chemistry, associate professor

109 publications, 1 037 citations, 8 reviews

h-index: 17

Institute of Petrochemistry and Catalysis of the Ufa Federal Research Center of the Russian Academy of Sciences

Research interests

Asymmetric metal complex catalysis

Regenerative materials

3 citations

Kiselev Artem

5 publications, 60 citations

h-index: 4

National Research University Higher School of Economics

A.V. Topchiev Institute of Petrochemical Synthesis RAS

Research interests

Organometallic Chemistry

1 citation

Churakov Andrei

PhD in Chemistry

553 publications, 7 015 citations, 13 reviews

h-index: 37

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

1 citation

Afanaseva Anna

🤝

4 publications, 11 citations

h-index: 2

National Research University Higher School of Economics

A.V. Topchiev Institute of Petrochemical Synthesis RAS

Research interests

Green chemistry

Metathesis

Organometallic Chemistry

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Nifant'ev I. E. et al. Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism // Molecules. 2019. Vol. 24. No. 19. p. 3565.

GOST all authors (up to 50) Copy

Nifant'ev I. E., Vinogradov A., Vinogradov A., Karchevsky S., Ivchenko P. Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism // Molecules. 2019. Vol. 24. No. 19. p. 3565.

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RIS Copy

TY - JOUR

DO - 10.3390/molecules24193565

UR - https://www.mdpi.com/1420-3049/24/19/3565

TI - Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism

T2 - Molecules

AU - Nifant'ev, Ilya E.

AU - Vinogradov, Alexander

AU - Vinogradov, Alexey

AU - Karchevsky, Stanislav

AU - Ivchenko, Pavel

PY - 2019

DA - 2019/10/02

PB - MDPI

SP - 3565

IS - 19

VL - 24

PMID - 31581621

SN - 1420-3049

ER -

BibTex |

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BibTex (up to 50 authors) Copy

@article{2019_Nifant'ev,

author = {Ilya E. Nifant'ev and Alexander Vinogradov and Alexey Vinogradov and Stanislav Karchevsky and Pavel Ivchenko},

title = {Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism},

journal = {Molecules},

year = {2019},

volume = {24},

publisher = {MDPI},

month = {oct},

url = {https://www.mdpi.com/1420-3049/24/19/3565},

number = {19},

pages = {3565},

doi = {10.3390/molecules24193565}

}

MLA

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MLA Copy

Nifant'ev, Ilya E., et al. “Zirconocene-catalyzed dimerization of α-Olefins: DFT modeling of the Zr-Al binuclear reaction mechanism.” Molecules, vol. 24, no. 19, Oct. 2019, p. 3565. https://www.mdpi.com/1420-3049/24/19/3565.

Publisher

MDPI

Journal

Molecules

scimago Q1

wos Q2

SJR

0.865

CiteScore

8.6

Impact factor

4.6

ISSN

14203049 (Print, Electronic)

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