A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques

A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques

1. Dr. F. Mark Chadwick, 
2. Dr. Nicholas H. Rees, 
3. Prof. Andrew S. Weller, 
4. Dr. Tobias Krämer, 
5. Dr. Marcella Iannuzziand
6. Prof. Stuart A. Macgregor
7. 1. 
      

Authors

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Chadwick, F. M., Rees, N. H., Weller, A. S., Krämer, T., Iannuzzi, M. and Macgregor, S. A. (2016), A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques. Angew. Chem. Int. Ed..

DOI: 10.1002/anie.201511269

Abstract

The pentane σ-complex [Rh{Cy₂P(CH₂CH₂)PCy₂}(η²:η²-C₅H₁₂)][BAr^F₄] is synthesized by a solid/gas single-crystal to single-crystal transformation by addition of H₂ to a precursor 1,3-pentadiene complex. Characterization by low temperature single-crystal X-ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4-positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature-dependent pentane rearrangement implicated by the SSNMR data.