Year: 2025
Type: article
Abstract: Four cis ‐chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel Ni II or Pd II 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 2 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 4 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.
Source: Chemistry - A European Journal
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
Awards: G5006681521, G7245920883
OpenAlex ID: W4410220511