Combined Experimental and Computational Studies on the Nature of Aromatic C-H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies Metadata

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Title

  • Main Title Combined Experimental and Computational Studies on the Nature of Aromatic C-H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies

Creator

  • Author: DeYonker, Nathan J.
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Foley, Nicholas A.
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Cundari, Thomas R., 1964-
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Gunnoe, T. Brent
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Petersen, Jeffrey L.
    Creator Type: Personal
    Creator Info: West Virginia University

Publisher

  • Name: American Chemical Society
    Place of Publication: [Washington, DC]

Date

  • Creation: 2007-11-27

Language

  • English

Description

  • Content Description: Article discussing combined experimental and computational studies on the nature of aromatic C-H activation by octahedral ruthenium(II) complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3].
  • Physical Description: 8 p.

Subject

  • Keyword: octahedral ruthenium
  • Keyword: Hammett correlatioin
  • Keyword: arene C-H bonds

Source

  • Journal: Organometallics, 2007, Washington DC: American Chemical Society, pp. 6604-6611

Citation

  • Publication Title: Organometallics
  • Volume: 26
  • Issue: 26
  • Page Start: 6604
  • Page End: 6611
  • Peer Reviewed: True

Collection

  • Name: UNT Scholarly Works
    Code: UNTSW

Institution

  • Name: UNT College of Arts and Sciences
    Code: UNTCAS

Rights

  • Rights Access: public

Resource Type

  • Article

Format

  • Text

Identifier

  • DOI: 10.1021/om7009057
  • Archival Resource Key: ark:/67531/metadc83332

Degree

  • Academic Department: Chemistry
  • Academic Department: Center for Advanced Scientific Computing and Modeling

Note

  • Display Note: Reprinted with permission from Organometallics. Copyright 2007 American Chemical Society.
  • Display Note: Abstract: Octahedral ruthenium complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3] have been shown previously to initiate the C-H activation of aromatic substrates. In order to probe the nature of the C-H activation step, reaction rates have been theoretically obtained for the conversion of TpRu(L)(ƞ2-C,C-C6H5X)Me to TpRu(L)(ρ-C6H4X) and CH4 where X is varied among Br, Cl, CN, F, H, NH2, NO2, and OMe. A linear Hammett correlation is calculated with a positive ρ value of 2.6 for L = CO and 3.2 for L = PMe3. Calculated kinetic data for the aromatic C-H activations indicate that an electrophilic aromatic substitution mechanism is unlikely. While experiments cannot fully replicate the entire range of calculated Hammett plots, reactivity trends are consistent with the calculations that suggest activation barriers to overall metal-mediated arene C-H bond cleavage are reduced by the presence of electron-withdrawing groups in the position para to the site of activation. Previous mechanistic studies, as well as the structure and imaginary vibrational modes of the present transition states, validate that the C-H activation for this family of TpRu complexes occurs through a σ-bond metathesis-type pathway.
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