<i>Cis</i> ‐Chelating Diphosphanes for Intracavity Nickel(II)‐Catalyzed Ethylene Oligomerization

Four cis-chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel Ni<sup>II</sup> or Pd<sup>II</sup> metal centers to reside within α- or β-CD cavities. Nickel(II) complexes of these metal-confining ligands act as active catalysts in ethylene oligomerization upon activation with modified methylaluminoxane (MMAO). The size of the cavity and the position of the P<sub>2</sub>Ni fragment relative to the cavity affect both the activity and selectivity of the reaction. In all instances, 1-butene is the major product (up to 98% C4 products and 90% 1-butene within the C<sub>4</sub> fraction). Extensive theoretical studies with state-of-the-art methods carried out on the most selective system suggest that the CD cavity restricts isomerization pathways by limiting the mobility of the coordinated olefin in this constrained supramolecular environment, thereby enhancing α-olefin formation.

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Publication Details

Journal
Chemistry - A European Journal
Published
2025-05-09
DOI
https://doi.org/10.1002/chem.202501188
Primary Topic
Molecular Junctions and Nanostructures
Type
article
Field-Weighted Citation Impact
0.00

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article

Cis ‐Chelating Diphosphanes for Intracavity Nickel(II)‐Catalyzed Ethylene Oligomerization

Tuan‐Anh Phan, Yang Li, Yann Cornaton, Matthieu Jouffroy et al.
Chemistry - A European Journal
Molecular Junctions and Nanostructures
article

Cis ‐Chelating Diphosphanes for Intracavity Nickel(II)‐Catalyzed Ethylene Oligomerization

Tuan‐Anh Phan, Yang Li, Yann Cornaton, Matthieu Jouffroy, Dominique Armspach, Jean‐Pierre Djukic, Sara Figueirêdo de Alcântara Morais, Pierre Braunstein, Katrin Pelzer, Mingyang Han, Dominique Matt, Geordie Creste
article en

Abstract

Four cis-chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel Ni<sup>II</sup> or Pd<sup>II</sup> metal centers to reside within α- or β-CD cavities. Nickel(II) complexes of these metal-confining ligands act as active catalysts in ethylene oligomerization upon activation with modified methylaluminoxane (MMAO). The size of the cavity and the position of the P<sub>2</sub>Ni fragment relative to the cavity affect both the activity and selectivity of the reaction. In all instances, 1-butene is the major product (up to 98% C4 products and 90% 1-butene within the C<sub>4</sub> fraction). Extensive theoretical studies with state-of-the-art methods carried out on the most selective system suggest that the CD cavity restricts isomerization pathways by limiting the mobility of the coordinated olefin in this constrained supramolecular environment, thereby enhancing α-olefin formation.

Chemistry - A European JournalVol. 31(34)
Centre National de la Recherche Scientifique (FR), Institut de Chimie de Strasbourg (FR), Catalyse (FR), Laboratoire de Chimie (FR), Université de Strasbourg (FR)
Chinese Academy of Sciences, China Scholarship Council, Grand Équipement National De Calcul Intensif, University of Chinese Academy of Sciences
Clean water and sanitation
Openalex Percentile: Top 92%
Molecular Junctions and Nanostructures
DOIOpen Access PDFOpenAlex
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