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  Switching the Spin State of Diphenylcarbene via Halogen Bonding

Henkel, S., Costa, P., Klute, L., Sokkar, P., Fernandez-Oliva, M., Thiel, W., et al. (2016). Switching the Spin State of Diphenylcarbene via Halogen Bonding. Journal of the American Chemical Society, 138(5), 1689-1697. doi:10.1021/jacs.5b12726.

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ja5b12726_si_001-1.pdf (Supplementary material), 3MB
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 Creators:
Henkel, Stefan1, Author
Costa, Paolo1, Author
Klute, Linda1, Author
Sokkar, Pandian2, Author              
Fernandez-Oliva, Miguel2, Author              
Thiel, Walter3, Author              
Sanchez-Garcia, Elsa2, Author              
Sander, Wolfram1, Author
Affiliations:
1Uni Bochum, ou_persistent22              
2Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1950289              
3Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Abstract: The interactions between diphenylcarbene DPC and the halogen bond donors CF3I and CF3Br were investigated using matrix isolation spectroscopy (IR, UV-vis, and EPR) in combination with QM and QM/MM calculations. Both halogen bond donors CF3X form very strong complexes with the singlet state of DPC, but only weakly interact with triplet DPC. This results in a switching of the spin state of DPC, the singlet complexes becoming more stable than the triplet complexes. CF3I forms a second complex (type II) with DPC that is thermodynamically slightly more stable. Calculations predict that in this second complex the DPC···I distance is shorter than the F3C···I distance, whereas in the first (type I) complex the DPC···I distance is, as expected, longer. CF3Br only forms the type I complex. Upon irradiation I or Br, respectively, are transferred to the DPC carbene center and radical pairs are formed. Finally, on annealing, the formal C-X insertion product of DPC is observed. Thus, halogen bonding is a powerful new principle to control the spin state of reactive carbenes.

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Language(s): eng - English
 Dates: 2015-12-052016-01-132016-02-10
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b12726
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 138 (5) Sequence Number: - Start / End Page: 1689 - 1697 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870