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Title: Rhodium complexes of sterically demanding diphosphonites: Coordination chemistry and catalysis
Authors: van der Vlugt, JI
Sablong, R
Magusin, Pieter
Mills, AM
Spek, AL
Vogt, D # ×
Issue Date: 2004
Publisher: American Chemical Society
Series Title: Organometallics vol:23 issue:13 pages:3177-3183
Abstract: The coordination chemistry of various sterically constrained diphosphonites 1-6 with rhodium are reported. The stoichiometric reaction of ligand 5 with [Rh(í-Cl(CO)2]2 gives rise to the sole formation of trans-[RhCl(CO)(5)] (7), as shown by NMR and IR spectroscopy and X-ray crystallography. The molecular structure reveals a weak interaction between the metal center and the oxygen from the xanthene backbone. This complex serves as a structural
model for the first intermediate in the catalytic cycle of rhodium hydroformylation, [Rh(H)-(CO)(PkP)]. A detailed study on the solution structure of the catalyst resting state under catalytic conditions is performed by high-pressure NMR and FT-IR spectroscopy. The spectroscopic data show that under hydroformylation conditions the bidentate ligands form well-defined complexes with the structure [Rh(H)(CO)2(PkP)]. All ligands show preference for a bis-equatorial (ee) coordination mode in the trigonal-bipyramidal Rh complexes. These novel sterically constrained diphosphonite ligands are applied in the rhodium hydroformylation of 1-octene and 2-butene, and good activities and regioselectivities are obtained.
ISSN: 0276-7333
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Non-KU Leuven Association publications
× corresponding author
# (joint) last author

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