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

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.

Creator(s):
Creation Date: May 9, 2007
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Total Uses: 241
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Creator (Author):
Foley, Nicholas A.

North Carolina State University

Creator (Author):
Lail, Marty

North Carolina State University

Creator (Author):
Lee, John P.

North Carolina State University

Creator (Author):
Gunnoe, T. Brent

North Carolina State University

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

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Petersen, Jeffrey L.

West Virginia University

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: May 9, 2007
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.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2007 American Chemical Society.

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.

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17 p.

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Subject(s):
Keyword(s): benzene | C-H activation | catalytic ethylene hydrophenylation | catalytic production | isotopic labeling | kinetic studies | reversible dissociation
Source: Journal of the American Chemical Society, 2007, Washington DC: American Chemical Society, pp. 6765-6781
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja068542p |
  • ARK: ark:/67531/metadc77140
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 129
Page Start: 6765
Page End: 6781
Pages: 17
Peer Reviewed: Yes