Phosphonate-Mediated Immobilization of Rhodium/Bipyridine Hydrogenation Catalysts

Chemistry. 2018 Feb 16;24(10):2457-2465. doi: 10.1002/chem.201705283. Epub 2018 Jan 25.

Abstract

RhL2 complexes of phosphonate-derivatized 2,2'-bipyridine (bpy) ligands L were immobilized on titanium oxide particles generated in situ. Depending on the structure of the bipy ligand-number of tethers (1 or 2) to which the phosphonate end groups are attached and their location on the 2,2'-bipyridine backbone (4,4'-, 5,5'-, or 6,6'-positions)-the resulting supported catalysts showed comparable chemoselectivity but different kinetics for the hydrogenation of 6-methyl-5-hepten-2-one under hydrogen pressure. Characterization of the six supported catalysts suggested that the intrinsic geometry of each of the phosphonate-derivatized 2,2'-bipyridines leads to supported catalysts with different microstructures and different arrangements of the RhL2 species at the surface of the solid, which thereby affect their reactivity.

Keywords: N ligands; hydrogenation; immobilization; rhodium; supported catalysts.