Chadwick, F. Mark, Krämer, Tobias, Gutmann, Torsten et al. (6 more authors) (2016) Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. Journal of the American Chemical Society. pp. 13369-13378. ISSN 1520-5126
Abstract
The controlled catalytic functionalization of alkanes via the activation of C-H bonds is a significant challenge. Although C-H activation by transition metal catalysts is often suggested to operate via intermediate σ-alkane complexes, such transient species are difficult to observe due to their instability in solution. This instability may be controlled by use of solid/gas synthetic techniques that enable the isolation of single-crystals of well-defined σ-alkane complexes. Here we show that, using this unique platform, selective alkane C-H activation occurs, as probed by H/D exchange using D2, and that five different isotopomers/isotopologues of the σ-alkane complex result, as characterized by single-crystal neutron diffraction studies for three examples. Low-energy fluxional processes associated with the σ-alkane ligand are identified using variable-temperature X-ray diffraction, solid-state NMR spectroscopy, and periodic DFT calculations. These observations connect σ-alkane complexes with their C-H activated products, and demonstrate that alkane-ligand mobility, and selective C-H activation, are possible when these processes occur in the constrained environment of the solid-state.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 American Chemical Society |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Arts and Humanities (York) > Archaeology (York) The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 03 Jan 2020 12:30 |
Last Modified: | 01 Nov 2024 01:21 |
Published Version: | https://doi.org/10.1021/jacs.6b07968 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.6b07968 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:155088 |
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Description: Selective C−H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange
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