In homogeneous catalysis, a C2-symmetric ligands usually describes bidentate ligands that are dyssymmetric but not asymmetric by virtue of their C2-symmetry. Such ligands have proven valuable in catalysis. With C2 symmetry, C2-symmetric ligands limit the number of possible reaction pathways and thereby increase enantioselectivity, at least relative to asymmetrical analogues. Most chiral ligands combine with metals to form chiral catalyst engages in a chemical reaction in which chirality is transfer to the reaction product.
The first such ligand, the diphosphine DiPAMP, was developed in 1968 by William S. Knowles and coworkers of Monsanto Company, who shared the 2001 Nobel Prize in Chemistry. This ligand was used in the industrial production of L-DOPA.
C2-symmetric diene ligand.
Both bi- and tridentate bis(oxazoline) ligands are used in organic synthesis
Both enantiomers of BINAP
BINOL, another binaphthalene-based ligand
DIPAMP, a diphosphine of historic significance
While the presence of any symmetry element within a ligand intended for asymmetric induction might appear counterintuitive, asymmetric induction only requires that the ligand be chiral (i.e. have no improper rotation axis). Asymmetric (i.e. absence of any symmetry elements) is not required. C2‑symmetry improves the enantioselectivity of the complex by reducing the number of transition states with a unique geometry. Steric/kinetic factors then usually favour the formation of a single product.
Chiral ligands work asymmetric induction somewhere along the reaction coordinate. The image depicted on the right gives a general idea how a chiral ligand may induce an enantioselective reaction. The ligand (in green) has C2 symmetry with its nitrogen, oxygen or phosphorus atoms hugging a central metal atom (in red). In this particular ligand the right side is sticking out and its left side points away. The substrate in this reduction is acetophenone and the reagent (in blue) a hydride ion. In absence of the metal and the ligand the re face approach of the hydride ion gives the (S)-enantiomer and the si face approach the (R)-enantiomer in equal amounts (a racemic mixture like expected). The ligand/metal presence changes all that. The carbonyl group will coordinate with the metal and due to the steric bulk of the phenyl group it will only be able to do so with its si face exposed to the hydride ion with in the ideal situation exclusive formation of the (R) enantiomer. The re face will simply hit the chiral fence. Note that when the ligand is replaced by its mirror image the other enantiomer will form and that a racemic mixture of ligand will once again yield a racemic product. Also note that if the steric bulk of both carbonyl substituents is very similar the strategy will fail.
Other C2-symmetric complexes
Many C2-symmetric complexes are known. Some arise, not from C2-symmetric ligands, but from the orientation or disposition of high symmetry ligands within the coordination sphere of the metal. Notably EDTA and triethylenetetraamine form complexes that are C2-symmetric by virtue of the way the ligands wrap around the metal centers. Two isomers are possible for (indenyl)2MX2, Cs- and C2-symmetric. The C2-symmetric complexes are optically stable.
(indenyl)2ZrMe2 viewed down C2 symmetry axis
C2-symmetric metal–EDTA chelate as found in Co(III) complexes.
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