Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange

F. Mark Chadwick, Tobias Krämer, Torsten Gutmann, Nicholas H. Rees, Amber L. Thompson, Alison J. Edwards, Gerd Buntkowsky, Stuart Alan Macgregor, Andrew S. Weller

Research output: Contribution to journalArticle

18 Citations (Scopus)
34 Downloads (Pure)

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.

Original languageEnglish
Pages (from-to)13369-13378
Number of pages10
JournalJournal of the American Chemical Society
Volume138
Issue number40
Early online date15 Sep 2016
DOIs
Publication statusPublished - 12 Oct 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange'. Together they form a unique fingerprint.

  • Cite this

    Chadwick, F. M., Krämer, T., Gutmann, T., Rees, N. H., Thompson, A. L., Edwards, A. J., Buntkowsky, G., Macgregor, S. A., & 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. Journal of the American Chemical Society, 138(40), 13369-13378. https://doi.org/10.1021/jacs.6b07968