Solid-state Synthesis And Characterization Of σ-alkane Complexes ...

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Journal article

Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = bidentate chelating phosphine)

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)(η(2),η(2)-C7H12)][BAr(F)4]; R = Cy, n = 2; R = (i)Pr, 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 (1)H 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 (31)P NMR data consistent with their formation, but they are now much less persistent at 298 K and ultimately give the corresponding zwitterions in which [BAr(F)4](-) coordinates and NBA is lost. The solid-state structures, as determined by X-ray crystallography, for all these [BAr(F)4](-) 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. Publication status: Published Peer review status: Peer reviewed

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  APA Style

  Pike, S., Chadwick, F., Rees, N., Scott, M., Weller, A., Krämer, T., & Macgregor, S. (2014). Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = bidentate chelating phosphine). Journal of the American Chemical Society, 137(2), 820–833. Copy APA Style

  MLA Style

  Pike, S., et al. “Solid-State Synthesis and Characterization of σ-Alkane Complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = Bidentate Chelating Phosphine).” Journal of the American Chemical Society, vol. 137, no. 2, American Chemical Society, 2014, pp. 820–33. Copy MLA Style

  Chicago Style

  Pike, S, F Chadwick, N Rees, M Scott, A Weller, T Krämer, and S Macgregor. 2014. “Solid-State Synthesis and Characterization of σ-Alkane Complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = Bidentate Chelating Phosphine).” Journal of the American Chemical Society 137 (2): 820–33. Copy Chicago Style

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Authors

+ Pike, S More by this author Role: Author + Chadwick, F More by this author Role: Author + Rees, N More by this author Institution: University of Oxford Division: MPLS Department: Chemistry Sub department: Inorganic Chemistry Role: Author + Scott, M More by this author Role: Author + Weller, A More by this author Institution: University of Oxford Oxford college: Magdalen College Role: Author Expand all More authors...

Funding

+ Engineering and Physical Sciences Research Council More from this funder

Bibliographic Details

Publisher: American Chemical Society Journal: Journal of the American Chemical Society More from this journal Volume: 137 Issue: 2 Pages: 820–833 Publication date: 2014-12-15 DOI: 10.1021/ja510437p ISSN: 1520-5126 and 0002-7863 Pmid: 25506741

Item Description

Language: English Keywords: SBTMR Pubs id: pubs:505138 UUID: uuid:82359fab-635d-459b-ab36-ea9a99c9a6f9 Local pid: pubs:505138 Source identifiers: 505138 Deposit date: 2017-03-01

Terms of use

Copyright holder: American Chemical Society Copyright date: 2014 Notes: This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Licence: Terms and Conditions of Use for Oxford University Research Archive

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