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A Rhodium–Pentane Sigma‐Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques
Author(s) -
Chadwick F. Mark,
Rees Nicholas H.,
Weller Andrew S.,
Krämer Tobias,
Iannuzzi Marcella,
Macgregor Stuart A.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201511269
Subject(s) - pentane , rhodium , alkane , chemistry , crystallography , crystal structure , single crystal , characterization (materials science) , x ray crystallography , stereochemistry , diffraction , materials science , catalysis , organic chemistry , nanotechnology , physics , optics
Abstract 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.