title: A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques.
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.
authors.affiliation: Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: F Mark
authors.initials: FM
authors.lastname: Chadwick
authors.affiliation: Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Nicholas H
authors.initials: NH
authors.lastname: Rees
authors.affiliation: Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK. andrew.weller@chem.ox.ac.uk.
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Weller
authors.affiliation: Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
authors.forename: Tobias
authors.initials: T
authors.lastname: Krämer
authors.affiliation: Physical-Chemistry Institute, University of Zürich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.
authors.forename: Marcella
authors.initials: M
authors.lastname: Iannuzzi
authors.affiliation: Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK. s.a.macgregor@hw.ac.uk.
authors.forename: Stuart A
authors.initials: SA
authors.lastname: Macgregor
keywords: C−H activation; alkanes; computation; rhodium; sigma complexes