Imperial College London
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Dr F. Mark Chadwick

Faculty of Natural Sciences, Department of Chemistry

Research Fellow
 
 
 
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Contact

 

+44 (0)20 7594 5872m.chadwick

 
 
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Location

 

601KMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Chadwick:2016:10.1021/jacs.6b07968,
author = {Chadwick, FM and Kramer, T and Gutmann, T and Rees, NH and Thompson, AL and Edwards, AJ and Buntkowsky, G and Macgregor, SA and Weller, AS},
doi = {10.1021/jacs.6b07968},
journal = {Journal of the American Chemical Society},
pages = {13369--13378},
title = {Selective C-H activation at a molecular rhodium sigma-alkane complex by solid/gas single-crystal to single-crystal H/D exchange},
url = {http://dx.doi.org/10.1021/jacs.6b07968},
volume = {138},
year = {2016}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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.
AU  - Chadwick,FM
AU  - Kramer,T
AU  - Gutmann,T
AU  - Rees,NH
AU  - Thompson,AL
AU  - Edwards,AJ
AU  - Buntkowsky,G
AU  - Macgregor,SA
AU  - Weller,AS
DO  - 10.1021/jacs.6b07968
EP  - 13378
PY  - 2016///
SN  - 0002-7863
SP  - 13369
TI  - Selective C-H activation at a molecular rhodium sigma-alkane complex by solid/gas single-crystal to single-crystal H/D exchange
T2  - Journal of the American Chemical Society
UR  - http://dx.doi.org/10.1021/jacs.6b07968
UR  - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000385469600043&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - https://pubs.acs.org/doi/10.1021/jacs.6b07968
UR  - http://hdl.handle.net/10044/1/85971
VL  - 138
ER  -
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