Furfari, Samantha K., Tegner, Bengt E., Burnage, Arron L. et al. (4 more authors) (2021) Selectivity of Rh⋅⋅⋅H−C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State. Chemistry : A European Journal. pp. 3177-3183. ISSN 1521-3765
Abstract
By using single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques, the σ -alkane complex [Rh( t Bu 2 PCH 2 CH 2 CH 2 P t Bu 2 )( η 2 , η 2 -C 7 H 12 )][BAr F 4 ] (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) is synthesized and structurally characterized, in which the alkane (norbornane) binds through two exo -C-H···Rh interactions. In contrast, the bis-cyclohexyl phosphine analogue shows endo -alkane binding. Comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, trace this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ -alkane complex is also a catalyst for solid/gas 1-butene isomerization, and catalyst resting states are identified for this.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Funding Information: We are grateful to SCG Chemicals, the EPSRC (M024210) and the Leverhulme Trust (RPG‐2015‐447) for funding; Professor Neil Champness (University of Nottingham, UK) for useful discussions and alerting us to the use of CrystalExplorer to explore weak interactions in the solid state; and Dr José Manuel Menéndez (Heriot‐Watt) for excellent IT support. Publisher Copyright: © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH |
Keywords: | density functional calculations,isomerization,periodic DFT,rhodium,selectivity,SMOM |
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/M024210/2 UNSPECIFIED RPG-2015-447 |
Depositing User: | Pure (York) |
Date Deposited: | 28 Oct 2020 14:50 |
Last Modified: | 07 Dec 2024 00:19 |
Published Version: | https://doi.org/10.1002/chem.202004585 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1002/chem.202004585 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:167349 |