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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- 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
Author: Foley, Nicholas A.Creator Type: PersonalCreator Info: North Carolina State University
Author: Lail, MartyCreator Type: PersonalCreator Info: North Carolina State University
Author: Lee, John P.Creator Type: PersonalCreator Info: North Carolina State University
Author: Gunnoe, T. BrentCreator Type: PersonalCreator Info: North Carolina State University
Author: Cundari, Thomas R., 1964-Creator Type: PersonalCreator Info: University of North Texas
Author: Petersen, Jeffrey L.Creator Type: PersonalCreator Info: West Virginia University
Name: American Chemical SocietyPlace of Publication: [Washington, DC]
- Creation: 2007-05-09
- 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.
- Keyword: benzene
- Keyword: C-H activation
- Keyword: catalytic ethylene hydrophenylation
- Keyword: catalytic production
- Keyword: isotopic labeling
- Keyword: kinetic studies
- Keyword: reversible dissociation
- Journal: Journal of the American Chemical Society, 2007, Washington DC: American Chemical Society, pp. 6765-6781
- Publication Title: Journal of the American Chemical Society
- Volume: 129
- Page Start: 6765
- Page End: 6781
- Pages: 17
- Peer Reviewed: True
Name: UNT Scholarly WorksCode: UNTSW
Name: UNT College of Arts and SciencesCode: UNTCAS
- Rights Access: public
- DOI: 10.1021/ja068542p
- Archival Resource Key: ark:/67531/metadc77140
- Academic Department: Chemistry
- Academic Department: Center for Advanced Scientific Computing and Modeling
- 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.