Probing the stereo-electronic properties of cationic rhodium complexes bearing chiral diphosphine ligands by 103Rh NMR

2010 John Wiley & Sons, Ltd.

Bibliographische Detailangaben
Veröffentlicht in:Magnetic resonance in chemistry : MRC. - 1985. - 48(2010), 11 vom: 01. Nov., Seite 848-56
1. Verfasser: Fabrello, Amandine (VerfasserIn)
Weitere Verfasser: Dinoi, Chiara, Perrin, Lionel, Kalck, Philippe, Maron, Laurent, Urrutigoity, Martine, Dechy-Cabaret, Odile
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2010
Zugriff auf das übergeordnete Werk:Magnetic resonance in chemistry : MRC
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Cations Ligands Organometallic Compounds Phosphines Rhodium DMK383DSAC
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520 |a (103)Rh NMR represents a powerful tool to assess the global electronic and steric contribution of diphosphine ligands on [Rh(COD)(diphosphine)](+) complexes. In the case of DIOP, BINAP and MeDUPHOS, this approach proved to be more informative than classical CO-stretching frequency measurements. After validation, this method has been extended to a set of seven diphosphines. (103)Rh NMR measurements on [Rh(COD)(diphosphine)]PF(6) lead to the following order of donor properties: dppe > MeBPE > MeDUPHOS > dppb > DIOP > BINAP > Tol-BINAP. This trend has been validated by DFT in the case of DIOP, BINAP and MeDUPHOS. In conjunction, (31)P NMR chemical shift has been shown to reflect the ring constraints of the Rh-diphosphine scaffold. This contribution is a step towards a mechanistic investigation of the catalytic hydrogenation of unsaturated substrates by (103)Rh NMR and DFT 
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700 1 |a Dinoi, Chiara  |e verfasserin  |4 aut 
700 1 |a Perrin, Lionel  |e verfasserin  |4 aut 
700 1 |a Kalck, Philippe  |e verfasserin  |4 aut 
700 1 |a Maron, Laurent  |e verfasserin  |4 aut 
700 1 |a Urrutigoity, Martine  |e verfasserin  |4 aut 
700 1 |a Dechy-Cabaret, Odile  |e verfasserin  |4 aut 
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