Synthesis and characterization of a chiral, aza-15-crown-5-functionalized ferrocenyldiphosphine ligand for asymmetric catalysis
A chiral ferrocenyldiphosphine ligand that is functionalized with an aza crown ether, (S)-1-[(R)-1{prime},2-bis(diphenylphosphino)ferroceny]ethyl-1-aza-2,3-benzo-15-crown-5(1), has been synthesized. Both the resolved and racemic ligands react rapidly with Pt(II) precursors to form stable metal-ligand adducts; the complexes PtMeI(rac-1) and PtMe{sub 2}(rac-1) have been characterized crystallographically. Reaction of rac-1 with [Rh(NBD){sub 2}]OTf yields [Rh(NBD)(rac-1)]OTf. The three-dimensional solution structure of [Rh(NBD)(rac-1)]OTf has been determined by NOESY experiments and analysis using the two-dimensional conformer population analysis algorithm (2DCPA). The NOESY data reveal rapid, pairwise chemical exchange between vinyl protons. The complex [Rh(NBD)(rac-1)]OTf is a catalyst precursor for hydrogenation reactions. However, the authors demonstrate that the liability of the aza crown ether may limit the ability of these catalysts to control selectivity via secondary interactions.
- Research Organization:
- Univ. of Wisconsin, Madison, WI (US)
- OSTI ID:
- 20050906
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 6 Vol. 19; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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