Rh(I) coordination chemistry of hexacationic Dendriphos ligands and their application in hydroformylation catalysis

Dennis J. M. Snelders, Katharina Kunna, Christian Muller, Dieter Vogt, Gerard van Koten, Robertus J. M. Klein Gebbink

Research output: Contribution to journalArticlepeer-review


The coordination chemistry of hexacationic Dendriphos ligands L* with respect to Rh(I), as well as their application in Rh-catalyzed hydroformylation reactions, is described. Complexes of the type RhCl(CO)(L*)(2) were synthesized and characterized. The results show that Dendriphos ligands are weaker sigma-donors and/or stronger pi-acceptors compared to PPh3. The reaction of L* with [Rh(cod)(2)]BF4 in MeCN afforded monophosphine-Rh(I) complexes of the type Rh(cod)(MeCN)(L*), which points to the tendency of these ligands to form coordinatively unsaturated metal complexes. The catalytic performance of Dendriphos ligands in the Rh-catalyzed hydroformylation appeared to be dominated by steric effects arising from the large dendritic shells of these ligands. Furthermore, the possibility of tuning the catalytic activity and selectivity of the catalytic species, by changing the six counteranions of the hexacationic Dendriphos ligand, has been investigated. Changing the anions from BF4- to the chiral anions camp-horsulphonate or Delta-Trisphat did not render the hydroformylation reaction of styrene enantioselective, albeit small changes in its regioselectivity were observed. (C) 2010 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)1411-1420
Number of pages10
JournalTetrahedron: Asymmetry
Issue number11-12
Publication statusPublished - 23 Jun 2010

Cite this