{"doi":"10.1021/jacs.6b07968","title":"Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange","volume":138,"date_created":"2026-02-07T09:08:45Z","author":[{"full_name":"Chadwick, F. M.","last_name":"Chadwick","first_name":"F. M."},{"first_name":"T.","last_name":"Kramer","full_name":"Kramer, T."},{"first_name":"Torsten","last_name":"Gutmann","full_name":"Gutmann, Torsten","id":"118165"},{"first_name":"N. H.","full_name":"Rees, N. H.","last_name":"Rees"},{"full_name":"Thompson, A. L.","last_name":"Thompson","first_name":"A. L."},{"first_name":"A. J.","last_name":"Edwards","full_name":"Edwards, A. J."},{"last_name":"Buntkowsky","full_name":"Buntkowsky, G.","first_name":"G."},{"first_name":"S. A.","full_name":"Macgregor, S. A.","last_name":"Macgregor"},{"first_name":"A. S.","full_name":"Weller, A. S.","last_name":"Weller"}],"date_updated":"2026-02-17T16:18:43Z","intvolume":"       138","page":"13369–13378","citation":{"apa":"Chadwick, F. M., Kramer, T., Gutmann, T., Rees, N. H., Thompson, A. L., Edwards, A. J., Buntkowsky, G., Macgregor, S. A., &#38; Weller, A. S. (2016). Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. <i>Journal of the American Chemical Society</i>, <i>138</i>(40), 13369–13378. <a href=\"https://doi.org/10.1021/jacs.6b07968\">https://doi.org/10.1021/jacs.6b07968</a>","mla":"Chadwick, F. M., et al. “Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.” <i>Journal of the American Chemical Society</i>, vol. 138, no. 40, 2016, pp. 13369–13378, doi:<a href=\"https://doi.org/10.1021/jacs.6b07968\">10.1021/jacs.6b07968</a>.","short":"F.M. Chadwick, T. Kramer, T. Gutmann, N.H. Rees, A.L. Thompson, A.J. Edwards, G. Buntkowsky, S.A. Macgregor, A.S. Weller, Journal of the American Chemical Society 138 (2016) 13369–13378.","bibtex":"@article{Chadwick_Kramer_Gutmann_Rees_Thompson_Edwards_Buntkowsky_Macgregor_Weller_2016, title={Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange}, volume={138}, DOI={<a href=\"https://doi.org/10.1021/jacs.6b07968\">10.1021/jacs.6b07968</a>}, number={40}, journal={Journal of the American Chemical Society}, author={Chadwick, F. M. and Kramer, T. and Gutmann, Torsten and Rees, N. H. and Thompson, A. L. and Edwards, A. J. and Buntkowsky, G. and Macgregor, S. A. and Weller, A. S.}, year={2016}, pages={13369–13378} }","chicago":"Chadwick, F. M., T. Kramer, Torsten Gutmann, N. H. Rees, A. L. Thompson, A. J. Edwards, G. Buntkowsky, S. A. Macgregor, and A. S. Weller. “Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.” <i>Journal of the American Chemical Society</i> 138, no. 40 (2016): 13369–13378. <a href=\"https://doi.org/10.1021/jacs.6b07968\">https://doi.org/10.1021/jacs.6b07968</a>.","ieee":"F. M. Chadwick <i>et al.</i>, “Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange,” <i>Journal of the American Chemical Society</i>, vol. 138, no. 40, pp. 13369–13378, 2016, doi: <a href=\"https://doi.org/10.1021/jacs.6b07968\">10.1021/jacs.6b07968</a>.","ama":"Chadwick FM, Kramer T, Gutmann T, et al. Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. <i>Journal of the American Chemical Society</i>. 2016;138(40):13369–13378. doi:<a href=\"https://doi.org/10.1021/jacs.6b07968\">10.1021/jacs.6b07968</a>"},"year":"2016","issue":"40","language":[{"iso":"eng"}],"extern":"1","user_id":"100715","_id":"63939","status":"public","abstract":[{"text":"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 sigma-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 sigma-alkane complexes. Here we show that, using this unique platform, selective alkane C-H activation occurs, as probed by H/D exchange using D-2, and that five different isotopomers/isotopologues of the sigma-alkane complex result, as characterized by single-crystal neutron diffraction studies for three examples. Low-energy fluxional processes associated with the sigma-alkane ligand are identified using variable-temperature X-ray diffraction, solid-state NMR spectroscopy, and periodic DFT calculations. These observations connect sigma-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.","lang":"eng"}],"publication":"Journal of the American Chemical Society","type":"journal_article"}