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Octahedral [TpRu(PMe3)2OR]n+ Complexes (Tp = hydridotris(pyrazolyl)borate; R = H or Ph; n = 0 or 1): Reactions at Ru(II) and Ru(III) Oxidation States with Substrates that Possess Carbon-Hydrogen Bonds


This article discusses octahedral [TpRu(PMe3)2OR]n+ Complexes (Tp = hydridotris(pyrazolyl)borate.

Creation Date: September 15, 2006
UNT College of Arts and Sciences
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Creator (Author):
Feng, Yuee

North Carolina State University

Creator (Author):
Gunnoe, T. Brent

North Carolina State University

Creator (Author):
Grimes, Thomas V.

University of North Texas

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

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
  • Creation: September 15, 2006

This article discusses octahedral [TpRu(PMe3)2OR]n+ Complexes (Tp = hydridotris(pyrazolyl)borate.

Department: Chemistry

Reprinted with permission from Organometallics. Copyright 2006 American Chemical Society.


Abstract: The Ru(II) complexes TpRu(PMe3)2OR (R = H or Ph) react with excess phenylacetylene at elevated temperatures to produce the phenylacetylide complex TpRu(PMe3)2(C≡CPh). Kinetic studies indicate that the reaction of TpRu(PMe3)2OH and phenylacetylene likely proceeds through a pathway that involves TpRu(PMe3)2OTf as a catalyst. The reaction of TpRu(PMe3)2OH with 1,4-cyclohexadiene at elevated temperature forms benzene and TpRu(PMe3)2H, while TpRu(PMe3)2OPh does not react with 1,4-cyclohexadiene even after 20 days at 80 ˚C. The paramagnetic Ru(III) complex [TpRu(PMe3)2OH][OTf] is formed upon single-electron oxidation of TpRu(PMe3)2OH with AgOTf. Reactivity studies suggest that [TpRu(PMe3)2OH][OTf] initiates reactions, including hydrogen atom abstraction, with C-H bonds that have bond dissociation energy < 80 kcal/mol. Experimentally, the O-H bond strength of the Ru(II) cation [TpRu(PMe3)2(OH2)][OTf] is estimated to be between 82 and 85 kcal/mol, while computational studies yield a BDE of 84 kcal/mol, which are in reasonable agreement with the observed reactivity of [TpRu(PMe3)2OH]+.

Physical Description:

10 p.

Keyword(s): carbon-hydrogen bonds | phenylacetylene
Source: Organometallics, 2006, Washington DC: American Chemical Society, pp. 5456-5465
UNT College of Arts and Sciences
UNT Scholarly Works
  • DOI: 10.1021/om0606385 |
  • ARK: ark:/67531/metadc77187
Resource Type: Article
Format: Text
Access: Public
Publication Title: Organometallics
Volume: 25
Page Start: 5456
Page End: 5465
Pages: 10
Peer Reviewed: Yes