Chadwick, F. Mark ; Krämer, Tobias ; Gutmann, Torsten ; Rees, Nicholas H. ; Thompson, Amber L. ; Edwards, Alison J. ; Buntkowsky, Gerd ; Macgregor, Stuart A. ; Weller, Andrew S. (2016)
Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.
In: Journal of the American Chemical Society, 138 (40)
doi: 10.1021/jacs.6b07968
Artikel, Bibliographie
Dies ist die neueste Version dieses Eintrags.
Kurzbeschreibung (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.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2016 |
| Autor(en): | Chadwick, F. Mark ; Krämer, Tobias ; Gutmann, Torsten ; Rees, Nicholas H. ; Thompson, Amber L. ; Edwards, Alison J. ; Buntkowsky, Gerd ; Macgregor, Stuart A. ; Weller, Andrew S. |
| Art des Eintrags: | Bibliographie |
| Titel: | Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange |
| Sprache: | Englisch |
| Publikationsjahr: | 2016 |
| Verlag: | ACS Publications |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Journal of the American Chemical Society |
| Jahrgang/Volume einer Zeitschrift: | 138 |
| (Heft-)Nummer: | 40 |
| DOI: | 10.1021/jacs.6b07968 |
| Zugehörige Links: | |
| Kurzbeschreibung (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. |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie |
| Hinterlegungsdatum: | 02 Aug 2024 12:36 |
| Letzte Änderung: | 02 Aug 2024 12:36 |
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| Suche nach Titel in: | TUfind oder in Google |
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Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. (deposited 09 Sep 2021 13:16)
- Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. (deposited 02 Aug 2024 12:36) [Gegenwärtig angezeigt]
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