Comparative Reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): Impact of Ancillary Ligand L on Activation of Carbon-Hydrogen Bonds Including Catalytic Hydroarylation and Hydrovinylation/Oligomerization of Ethylene Metadata

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Title

  • Main Title Comparative Reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): Impact of Ancillary Ligand L on Activation of Carbon-Hydrogen Bonds Including Catalytic Hydroarylation and Hydrovinylation/Oligomerization of Ethylene

Creator

  • Author: Foley, Nicholas A.
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Lail, Marty
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Lee, John P.
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Gunnoe, T. Brent
    Creator Type: Personal
    Creator Info: North Carolina State University
  • Author: Cundari, Thomas R., 1964-
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Petersen, Jeffrey L.
    Creator Type: Personal
    Creator Info: West Virginia University

Publisher

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

Date

  • Creation: 2007-05-09

Language

  • English

Description

  • Content Description: Article discussing research on the comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3) and the impact of ancillary ligand L on activation of carbon-hydrogen bonds including catalytic hydroarylation and hyrdovinylation/oligomerization of ethylene.
  • Physical Description: 17 p.

Subject

  • Keyword: benzene
  • Keyword: C-H activation
  • Keyword: catalytic ethylene hydrophenylation
  • Keyword: catalytic production
  • Keyword: isotopic labeling
  • Keyword: kinetic studies
  • Keyword: reversible dissociation

Source

  • Journal: Journal of the American Chemical Society, 2007, Washington DC: American Chemical Society, pp. 6765-6781

Citation

  • Publication Title: Journal of the American Chemical Society
  • Volume: 129
  • Page Start: 6765
  • Page End: 6781
  • Pages: 17
  • 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/ja068542p
  • Archival Resource Key: ark:/67531/metadc77140

Degree

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

Note

  • Display Note: Reprinted with permission from the Journal of the American Chemical Society. Copyright 2007 American Chemical Society.
  • Display Note: Abstract: Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris-(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu-(PMe3)(ɳ3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(ɳ3-C4H7)(L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(ɳ3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes.