Catalytic and Structural Features of Hydroxy and Methoxy Groups as Hemilabile Coordinating Ligands in Chiral (Diphosphane)rhodium(I) Hydrogenation Catalysts

Half‐Sandwich Rhodium (and Iridium) Complexes as Enantioselective Catalysts for the 1,3‐Dipolar Cycloaddition of 3,4‐Dihydroisoquinoline N‐Oxide to Methacrylonitrile

“…Subsequent coordination of one of the resulting hydroxy groups affords complex 5 . It has been previously reported that the antipode ( R , R )‐Hyphos ligand is also κ 3 ‐ P , P , O coordinated in the rhodium complex [Rh(nbd){( S , S )‐Hyphos}]BF 4 (nbd=norbornadiene) 11…”

Chiral Oxo- and Oxy-Functionalized Diphosphane Ligands Derived from Camphor for Rhodium(I)-Catalyzed Enantioselective Hydrogenation

“…The presence of hydroxy and alkoxy groups in diphosphane ligands such as 3 ,5 4 (RoPHOS)6 and 5 (BASPHOS)7 were shown to influence − dramatically in some cases − the selectivity and activity of the Rh I catalysts. Mechanistic studies provided evidence that these effects might be caused by secondary interactions of the hydroxy groups with the metal centre or the substrate 8.…”

[1L-3,4-Bis-O-(diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol-κ2P,P′][η4-(Z,Z)-cycloocta-1,5-diene]rhodium(I) tetrafluoridoborate chloroform solvate

“…The COD rings have twisted boat conformations (Bats et al, 2004), and are skewed with regard to the RhP 2 plane, similar to the con®guration observed in, for example, CACNAW (Holz et al, 2001). A CSD survey of related (L)Rh(COD) + compounds, where L is a bis(phosphine) ligand linked into a seven-membered ring by four atoms (17 hits), shows that the COD-coordinated C atoms are always asymmetrically placed with respect to the RhP 2 plane [with bond mid-points from 0.06 to 0.60 A Ê out of the plane (PUHPAJ; Borns et al, 1998)]. In our case, the midpoint of one C C set is coplanar [the out-of-RhP 2 -plane values are 0.015 (8) and 0.033 (8) A Ê ], while the other set is 0.355 (8) and 0.248 (8) A Ê from the plane.…”