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Arthurs, Ross A., Prior, Christopher C., Hughes, David L., Oganesyan, Vasily S. 
ORCID: https://orcid.org/0000-0002-8738-1146 and Richards, Christopher J. ORCID: https://orcid.org/0000-0001-7899-4082
(2018)
Enantiopure planar chiral and chiral-at-metal iridacycles derived from bulky cobalt sandwich complexes.
Organometallics, 37 (22).
pp. 4204-4212.
ISSN 0276-7333
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Abstract
Reaction of (η5-(S)-2-(4-methylethyl)oxazolinylcyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt with [IrCp*Cl2]2 in acetonitrile with KPF6 and KOt-Bu resulted in S,Sp,SIr and S,Rp,RIr configured acetonitrile and Cp* coordinated cationic iridacycles (d.r. up to 4.8 : 1 – kinetic control), the planar chiral configuration dictating the configuration of the pseudo-tetrahedral iridium-based stereogenic centre. Addition of water to the cycloiridation reaction resulted in an increase in yield (up to 78%) at the cost of diastereoselectivity. Use of the corresponding substrate containing a t-Bu rather than an i-Pr substituted oxazoline gave exclusively the S,Sp,SIr diastereoisomer, and under the same conditions (S)-2-ferrocenyl- 4-(1,1-dimethylethyl)oxazoline cycloiridated to give only the S,Sp,SIr diastereoisomer. Substitution reactions of the title complexes at iridium proceeded with retention of configuration, a computational study revealing the proposed coordinatively unsaturated intermediate of a dissociative mechanism to display a relatively weak Co-Ir interaction, and a pronounced steric effect as the basis of stereocontrol.
| Item Type: | Article |
|---|---|
| Faculty \ School: | Faculty of Science > School of Chemistry |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Life Processes Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry Faculty of Science > Research Groups > Centre for Photonics and Quantum Science |
| Depositing User: | LivePure Connector |
| Date Deposited: | 04 Feb 2019 15:30 |
| Last Modified: | 13 May 2023 00:48 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/69836 |
| DOI: | 10.1021/acs.organomet.8b00495 |
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