Large cavity cyclodextrin-based macrocyclic ligands : synthesis, coordination and catalytic properties
type: Dataset
description: Cyclodextrins (CDs) are cyclic oligosaccharides of various sizes containing several α-(1→4)-linked D-(+)- glucopyranose units. The commercially available ones comprise six, seven or eight glucose units, named respectively α-CD, β-CD and γ-CD. Their truncated cone-like and well-defined cavity are particularly attractive for the encapsulation of a variety of substrates. As such, they found numerous applications in many areas of chemistry. A recent development, from which the present work is inspired, consisted in covalently linking transition metals to CD cavities in order to perform and study catalytic reactions in a confined environment featuring steric repulsive or attractive noncovalent interactions with the substrate or/and the metal coordination sphere.The first part of this thesis focuses on reviewing transition metal-based cavitands, for which the first and second metal coordination spheres are controlled by their cavity-shaped ligand. The following chapters are concerned with the synthesis, coordination and catalytic properties of two new phosphane ligands built on a large β-CD scaffold. The first one, named WIDEPHOS, is a diphosphine having two phenylphosphinidene "PPh" units capping adjacent glucose units on a methylated β-CD. This ligand features two phosphorus lone pairs pointing to the cavity interior but not aligned. These geometrical features, combined with the large distance separating the two phosphorus atoms, promote the formation of "imperfect" trans-chelate complexes in which the metal centre swings about the ligand. This unprecedented molecular movement, christened "oschelation", allows each phosphorus atom to form an optimal bond in turn with the coordinated d8 and d10 transition metal ions. Further studies on WIDEPHOS proved that it is better suited for coordinating dinuclear fragments within the confinement of the large β-CD cavity. Severe steric constrains on the metal first sphere of coordination result in the formation of single μ-chlorido …
landing page: https://theses.hal.science/tel-00767168
identifier: NNT: 2012STRAF007
keyword: cavitands
keyword: chimothechemical-sciencesother
keyword: complexes-chelates
keyword: complexes-dinucleaires
keyword: couplage-de-heck-mizoroki
keyword: cyclodextrines
keyword: cyclodextrins
keyword: diphosphines-trans-chelatantes
keyword: dynamique-moleculaire
keyword: infoeu-reposemanticsdoctoralthesis
keyword: theses
issued: 2026-05-30T04:37:45.463692
modified: 2026-05-30T04:37:45.463702
language: en
contact point: Organization
  fn: CCSD

test_moissonnage_selune
type: Agent

Large cavity cyclodextrin-based macrocyclic ligands : synthesis, coordination and catalytic properties
type: Distribution
format: HTML
access URL: https://theses.hal.science/tel-00767168
issued: 2026-05-30T04:37:45.576149
modified: 2026-05-30T04:37:45.417550