Size-Selective Hydroformylation by a Rhodium Catalyst Confined in a Supramolecular Cage.

ABSTRACT: Size-selective hydroformylation of terminal alkenes was attained upon embedding a rhodium bisphosphine complex in a supramolecular metal-organic cage that was formed by subcomponent self-assembly. The catalyst was bound in the cage by a ligand-template approach, in which pyridyl-zinc(II) porphyrin interactions led to high association constants (>10⁵  m^-1 ) for the binding of the ligands and the corresponding rhodium complex. DFT calculations confirm that the second coordination sphere forces the encapsulated active species to adopt the ee coordination geometry (i.e., both phosphine ligands in equatorial positions), in line with in situ high-pressure IR studies of the host-guest complex. The window aperture of the cage decreases slightly upon binding the catalyst. As a

SUBMITTER: Nurttila SS 

PROVIDER: S-EPMC6391983 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature