Sajjad, M. Arif, Macgregor, Stuart A. and Weller, Andrew S. orcid.org/0000-0003-1646-8081 (Accepted: 2023) A comparison of non-covalent interactions in the crystal structures of two σ-alkane complexes of Rh exhibiting contrasting stabilities in the solid state. FARADAY DISCUSSIONS. ISSN 1364-5498 (In Press)
Abstract
Non-covalent interactions surrounding the cationic Rh σ-alkane complexes within the crystal structures of [(Cy2PCH2CH2PCy2)Rh(NBA)][BArF4], [1-NBA][BArF4] (NBA = norbornane, C7H12; ArF = 3,5-(CF3)2C6H3), and [1-propane][BArF4] are analysed using Quantum Theory of Atoms in Molecules (QTAIM) and Independent Gradient Model approaches, the latter under a Hirshfeld partitioning scheme (IGMH). In both structures the cations reside in an octahedral array of [BArF4]− anions within which the [1-NBA]+ cation system exhibits a greater number of C-H⋯F contacts to the anions. QTAIM and IGMH analyses indicate these include the strongest individual atom-atom non-covalent interactions between the cation and the anion in these systems. The IGMH approach highlights the directionality of these C-H⋯F contacts that contrasts with the more diffuse C-H⋯π interactions. The accumulative effects of the latter lead to a more significant stabilizing contribution. IGMH %δGatom plots provide a particularly useful visual tool to identify key interactions and highlight the importance of a -{C3H6}- propylene moiety that is present within both the propane and NBA ligands (the latter as a truncated -{C3H4}- unit) and the cyclohexyl rings of the phosphine substituents. The potential for this to act as a privileged motif that confers stability on the crystal structures of σ-alkane complexes in the solid-state is discussed. The greater number of C-H⋯F inter-ion interactions in the [1-NBA][BArF4] system, coupled with more significant C-H⋯π interactions are all consistent with greater non-covalent stabilisation around the [1-NBA]+ cation. This is also supported by larger computed δGatom indices as a measure of cation-anion non-covalent interaction energy.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Funding Information: We thank the EPSRC for funding via awards EP/W015498/1 and EP/W015552/1. Publisher Copyright: © 2023 The Royal Society of Chemistry. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number EPSRC EP/W015552/1 |
Depositing User: | Pure (York) |
Date Deposited: | 31 Jan 2023 10:10 |
Last Modified: | 23 Oct 2024 00:18 |
Published Version: | https://doi.org/10.1039/D3FD00009E. |
Status: | In Press |
Refereed: | Yes |
Identification Number: | 10.1039/D3FD00009E. |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:195875 |