Chiral P,N-bidentate ligands in coordination chemistry and organic catalysis involving rhodium and palladium

Abstract

Published data on the synthesis of rhodium and palla-Published data on the synthesis of rhodium and palladium complexes with optically active P,N-bidentate ligands and dium complexes with optically active P,N-bidentate ligands and their applications in homogeneous asymmetric catalysis are their applications in homogeneous asymmetric catalysis are summarised and discussed. The effect of the nature of the P,N-summarised and discussed. The effect of the nature of the P,Nbidentate compounds on the structure of the metal complexes and bidentate compounds on the structure of the metal complexes and on enantioselectivity in catalysis is examined. Allylic substitution, on enantioselectivity in catalysis is examined. Allylic substitution, cross-coupling, hydroboration and hydrosilylation catalysed by cross-coupling, hydroboration and hydrosilylation catalysed by Rh or Pd complexes with optically active P,N-bidentate ligands Rh or Pd complexes with optically active P,N-bidentate ligands are considered. The prospects for the development of this field of are considered. The prospects for the development of this field of chemistry are demonstrated. The bibliography includes 186 refer-chemistry are demonstrated. The bibliography includes 186 references ences. .

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: New Mechanistic Insights Using D2O as Deuterium‐Labeling Agent

“…Control experiments were also carried out with PPh 3 and in the absence of phosphane ligand. In a previous contribution, we have reported the catalytic activity and linear/branched selectivity of the above systems in dry CHCl 3 . [18] The hydroformylation experiments in the presence of D 2 O, reported in this paper, were carried out under similar conditions with the exception of the solvent, which was changed from CHCl 3 to THF in order to insure homogeneous conditions in the presence of water.…”

“…[28][29][30] We could then evaluate their potential for extension to biphasic conditions. [31] Results and Discussion 3 ], in the presence of 1000 equivalents of D 2 O and styrene. Control experiments were also carried out with PPh 3 and in the absence of phosphane ligand.…”

“…Metal complexes containing P,N bifunctional phosphanes have attracted considerable attention in the field of homogeneous catalysis, in particular with transition metals like Ni, [1] Pd, [2,3] Pt, [4] Ru, [5,6] Rh, [3,7] and Ir. [8][9][10] These ligands can be either κ 1 :P or κ 2 :P,N coordinated and each coordination mode can modify the catalytic properties.…”

“…www.eurjic.orgAdditional catalytic runs were performed with complexes RhCl(COD)(S,S-α-P,N) and Rh(acac)(CO)(S,S -α-P,N) prepared in situ from the chiral ligand [S,S-α-P,N = (S Ar ,S C )-Ph 2 PCH{o-C 6 H 4 Cl(Cr(CO) 3 )}NHPh] [17] and the rhodium precatalysts [RhCl(COD)] 2 and Rh(acac)(CO) 2 , respectively. These tests, run either with RhCl(COD)(S,S-α-P,N) in CHCl 3 or with Rh(acac)(CO)(S,S-α-P,N) in C 6 H 6 , gave (S)-2-phenylpropanal with 7 and 14 % ee, respectively.…”

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

“…[1][2][3][4][5][6][7][8] These ligands can be either κ 1 -P or κ 2 -P,N coordinated and each coordination mode can modify the catalytic properties. For example, the chelating coordination mode enhances the nucleophilic character of the metal center and subsequently promotes hydrogen oxidative addition.…”