A Rhodium–Pentane Sigma‐Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques. (15th February 2016)

• Record Type: Journal Article
• Authors: Chadwick, F. Mark; Rees, Nicholas H.; Weller, Andrew S.; Krämer, Tobias; Iannuzzi, Marcella; Macgregor, Stuart A.
• Is Part Of: Angewandte Chemie. Volume 128:Number 11(2016)
• Page Start: 3741
• Page End: 3745
• Publication Date: 2016-02-15
• Subjects: Alkane -- C-H-Aktivierung -- Computerchemie -- Rhodium -- Sigma-Komplexe; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201511269
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The pentane σ‐complex [Rh{Cy2 P(CH2 CH2 )PCy2 }(η 2 :η 2 ‐C5 H12 )][BAr F 4 ] 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.