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

The pentane σ‐complex [Rh{Cy 2 P(CH 2 CH 2 )PCy 2 }(η 2 :η 2 ‐C 5 H 12 )][BAr F 4 ] is synthesized by a solid/gas single‐crystal to single‐crystal transformation by addition of H 2 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.