Burrows, KE orcid.org/0000-0002-5485-6256, Kulmaczewski, R orcid.org/0000-0002-3855-4530, Cespedes, O orcid.org/0000-0002-5249-9523 et al. (2 more authors) (2018) The Speciation of Homochiral and Heterochiral Diastereomers of Homoleptic Cobalt(II) and Zinc(II) PyBox Complexes. Polyhedron, 149. pp. 134-141. ISSN 0277-5387
Abstract
Homochiral [M((R)-LR)2]2+ and heterochiral [M((R)-LR)((S)-LR)]2+ isomers of [Zn(LPh)2][BF4]2, [Zn(LiPr)2][BF4]2, [Co(LPh)2][BF4]2, and [Co(LiPr)2][BF4]2 (LPh = 2,6-bis(4-phenyloxazolinyl)pyridine; LiPr = 2,6-bis(4-isopropyloxazolinyl)pyridine) have been prepared and characterised. Six of the eight compounds were crystallographically characterised, showing that steric repulsions between ligand substituents lead to more distorted coordination geometries in the homochiral isomers, especially in the LiPr complexes. Heterochiral [M((R)-LiPr)((S)-LiPr)]2+ (M = Zn or Co) undergoes partial racemisation in CD3CN through ligand redistribution reactions, whereas [M((R)-LPh)((S)-LPh)]2+ does not (in agreement with previous reports). This may be a consequence of intramolecular π... π - interactions in [M((R)-LPh)((S)-LPh)]2+, whereby each pyridyl group is sandwiched between two phenyl substituents from the other LPh ligand. These π... π -interactions are disrupted in homochiral [M((R)-LR)2]2+, owing to the aforementioned steric clash between phenyl substituents in that isomer.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 Elsevier Ltd. This is an author produced version of a paper published in Polyhedron. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | Zinc; Cobalt; N-donor ligands; Chirality; X-ray crystallography |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Physics and Astronomy (Leeds) > Condensed Matter (Leeds) |
Funding Information: | Funder Grant number EPSRC EP/K012568/1 Leverhulme Trust RPG-2015-095 |
Depositing User: | Symplectic Publications |
Date Deposited: | 04 May 2018 10:26 |
Last Modified: | 16 Dec 2024 15:15 |
Status: | Published |
Publisher: | Elsevier |
Identification Number: | 10.1016/j.poly.2018.04.030 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:130458 |