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Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η2,η2-C7H12)][BArF4] (L2 = bidentate chelating phosphine)
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Pike, Sebastian D., Chadwick, F. Mark, Rees, Nicholas H., Scott, Mark P., Weller, Andrew S., Krämer, Tobias and Macgregor, Stuart A. (2015) Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η2,η2-C7H12)][BArF4] (L2 = bidentate chelating phosphine). Journal of the American Chemical Society, 137 (2). pp. 820-833. doi:10.1021/ja510437p ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/ja510437p
Abstract
The use of solid/gas and single-crystal to single-crystal synthetic routes is reported for the synthesis and characterization of a number of σ-alkane complexes: [Rh(R2P(CH2)nPR2)(η2,η2-C7H12)][BArF4]; R = Cy, n = 2; R = iPr, n = 2,3; Ar = 3,5-C6H3(CF3)2. These norbornane adducts are formed by simple hydrogenation of the corresponding norbornadiene precursor in the solid state. For R = Cy (n = 2), the resulting complex is remarkably stable (months at 298 K), allowing for full characterization using single-crystal X-ray diffraction. The solid-state structure shows no disorder, and the structural metrics can be accurately determined, while the 1H chemical shifts of the Rh···H–C motif can be determined using solid-state NMR spectroscopy. DFT calculations show that the bonding between the metal fragment and the alkane can be best characterized as a three-center, two-electron interaction, of which σCH → Rh donation is the major component. The other alkane complexes exhibit solid-state 31P NMR data consistent with their formation, but they are now much less persistent at 298 K and ultimately give the corresponding zwitterions in which [BArF4]− coordinates and NBA is lost. The solid-state structures, as determined by X-ray crystallography, for all these [BArF4]− adducts are reported. DFT calculations suggest that the molecular zwitterions within these structures are all significantly more stable than their corresponding σ-alkane cations, suggesting that the solid-state motif has a strong influence on their observed relative stabilities.
Item Type: | Journal Article | |||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||
Library of Congress Subject Headings (LCSH): | Alkanes -- Synthesis, Chemical structure, Ligands, Solid state chemistry, X-ray crystallography | |||||||||
Journal or Publication Title: | Journal of the American Chemical Society | |||||||||
Publisher: | American Chemical Society | |||||||||
ISSN: | 0002-7863 | |||||||||
Official Date: | 21 January 2015 | |||||||||
Dates: |
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Volume: | 137 | |||||||||
Number: | 2 | |||||||||
Page Range: | pp. 820-833 | |||||||||
DOI: | 10.1021/ja510437p | |||||||||
Status: | Peer Reviewed | |||||||||
Publication Status: | Published | |||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||
RIOXX Funder/Project Grant: |
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