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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

Chadwick, F. Mark ; Krämer, Tobias ; Gutmann, Torsten ; Rees, Nicholas H. ; Thompson, Amber L. ; Edwards, Alison J. ; Buntkowsky, Gerd ; Macgregor, Stuart A. ; Weller, Andrew S. (2021):
Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. (Publisher's Version)
In: Journal of the American Chemical Society, 138 (40), pp. 13369-13378. ACS Publications, ISSN 0002-7863, e-ISSN 1520-5126,
DOI: 10.26083/tuprints-00018890,
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Item Type: Article
Origin: Secondary publication service
Status: Publisher's Version
Title: Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange
Language: English
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.

Journal or Publication Title: Journal of the American Chemical Society
Journal volume: 138
Number: 40
Publisher: ACS Publications
Classification DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Divisions: 07 Department of Chemistry > Physical Chemistry
Date Deposited: 09 Sep 2021 13:16
Last Modified: 09 Sep 2021 13:17
DOI: 10.26083/tuprints-00018890
Corresponding Links:
URN: urn:nbn:de:tuda-tuprints-188903
URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/18890
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