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- Title
Cavitand Chemistry - Towards Metallocapsular Catalysts.
- Authors
Chavagnan, Thierry; Sémeril, David; Matt, Dominique; Toupet, Loïc
- Abstract
Two diphosphanes with widely separated P centres and cores that consists of two covalently linked resorcinarene cavitands were synthesised. Their ability to bind transitionmetal ions in a chelating fashion with the concomitant formation of capsular complexes was shown in their reactions with metal centres with two available binding sites. The solid-state structure of one of the complexes, a capsule with a partially embedded "trans-PtCl2" unit, was determined by single-crystal X-ray diffraction. Upon reaction with SnCl2, this complex developed good activity for the hydroformylation of styrene. Its activity and selectivity towards the branched aldehyde were significantly superior to those observed for the reference complex trans-PtCl2L2, in which L is a monophosphane monocavitand ligand. The higher activity is likely to reflect the initial formation of a hydrido intermediate with a somewhat distorted trigonalbipyramidal structure that facilitates the intracapsular olefin/PtH insertion step. The observed aldehyde selectivity is probably controlled by the shape of the capsule, which is sterically better suited for hosting a branched Pt-alkyl unit than a linear one.
- Subjects
CAVITANDS; DIPHOSPHINE; CATALYSIS; MOLECULAR structure of ligands; PHOSPHINE synthesis; STYRENE
- Publication
European Journal of Organic Chemistry, 2017, Vol 2017, Issue 2, p313
- ISSN
1434-193X
- Publication type
Article
- DOI
10.1002/ejoc.201601278