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

F. Mark Chadwick; Nicholas H. Rees; Andrew S. Weller; Tobias Krämer; Marcella Iannuzzi; Stuart A. Macgregor

doi:10.1002/anie.201511269

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

F. Mark Chadwick, Nicholas H. Rees, Andrew S. Weller^*, Tobias Krämer, Marcella Iannuzzi, Stuart A. Macgregor

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The pentane σ-complex [Rh{Cy₂P(CH₂CH₂)PCy₂}(η²:η²-C₅H₁₂)][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.

Original language	English
Pages (from-to)	3677-3681
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	11
DOIs	https://doi.org/10.1002/anie.201511269
Publication status	Published - 7 Mar 2016

Keywords

alkanes
C-H activation
computation
rhodium
sigma complexes

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10.1002/anie.201511269

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title = "A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques",

abstract = "The pentane σ-complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2-C5H12)][BArF 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.",

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year = "2016",

month = mar,

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doi = "10.1002/anie.201511269",

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T1 - A Rhodium-Pentane Sigma-Alkane Complex

T2 - Characterization in the Solid State by Experimental and Computational Techniques

AU - Chadwick, F. Mark

AU - Rees, Nicholas H.

AU - Weller, Andrew S.

AU - Krämer, Tobias

AU - Iannuzzi, Marcella

AU - Macgregor, Stuart A.

PY - 2016/3/7

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N2 - The pentane σ-complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2-C5H12)][BArF 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.

AB - The pentane σ-complex [Rh{Cy2P(CH2CH2)PCy2}(η2:η2-C5H12)][BArF 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.

KW - alkanes

KW - C-H activation

KW - computation

KW - rhodium

KW - sigma complexes

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IS - 11

ER -

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

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Keywords

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