A Rhodium-Pentane sigma-alkane complex: Characterization in the solid state by experimental and computational techniques.

摘要

The pentane σ–complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2–C5H12)][BArF4] 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-raydiffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination via 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.