I am looking for some examples for the titled reactions.
In more detail of what I am looking for:
M*(LL)2(L'L') ----> M*(LL)2(L''L'')*
Where: LL, L'L' are bidentate ligands; L"L"* newly formed ligand with chiral center.
M: Metal ion; M* - chiral at metal (Delta/lamda);
So, reaction on coordinated ligand (not ligands exchange), and the chirality of the newly form L"L"* ligand (R or S) is determined by chirality of M*; overall reaction is diastereoselective.
It is common that chirality is transfer from ligand to metal. I need the other way around.
Can anyone help, please.
It relates to:
- Chirality of octahedral complexes (delta, lamda)
- Reaction of coordinated ligands
- And transfer of chiral information from chiral-at-metal to ligand.
Do you mean about chirality transfer from metal center to ligand ?
Ah, Yeah. Transfer chirality information from chiral metal center to ligand. If you have idea, a ref, a name of research group..., please share with me. I prefer octahedral metal center.
Thanks!
Bellow is a typical example of chirality transfering from Ligand to metal (credit: cc/c2cc31542d). I am looking for the other way around, metal to ligand.
Because the chirality at the metal center is created generally by chiral ligands, at this moment I cannot see other way than chirality transfer via ligand exchange (dissociation). You can separate diastereomers, which are also chiral at metal centrum but that is not your goal, isn't it. Complexes containing different achiral ligands, can also be chiral at the metal center, but a kinetic or dynamic kinetic resolution of these enantiomers is probably also not of your interest.
-Actually, the chiral-at-metal are delta/lamda isomer (the first chiral center), not because of ligand.
- Start with all achiral ligands, then reaction (addition, substitution, alkylation, metallation) happends on one of those achiral coordinated ligands -> convert it into the second chiral center.
- The chirality of 2nd center is determined by chirality of the 1st.
That is what i mean by transfer chirality from metal to ligands.
Thank you!
Please check the related articles.
1. Organometallics, 2006, 25, 2826-2832.
2. For octahedral complexes Inorg. Chem., 2003, 42 (16), 4810–4816.
3. Chem. Commun., 2001, 521–522.
4. J. Am. Chem. Soc., 1985, 107 (18), pp 5315–5317.
5. Inorg. Chem. 2004,43, 3329−3331.
Some more are there. You can get from cross refereneces.
Cheers
Thank you, Himanshu.
I just have a scan, some of them i've read throught before, some havent.
There are two points make it difficult to find.
- Reaction on coordinated ligand (not ligand exchange, but just "be modified")
- Kind of truely octahedral (vs half-sandwich).
Again, Thank you for your time.
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