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

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

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10 p.

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Feng, Yuee; Gunnoe, T. Brent; Grimes, Thomas V. & Cundari, Thomas R., 1964- September 15, 2006.

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

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10 p.

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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]+.

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  • Organometallics, 2006, Washington DC: American Chemical Society, pp. 5456-5465

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  • Publication Title: Organometallics
  • Volume: 25
  • Page Start: 5456
  • Page End: 5465
  • Pages: 10
  • Peer Reviewed: Yes

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  • September 15, 2006

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  • March 9, 2012, 2:17 p.m.

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Feng, Yuee; Gunnoe, T. Brent; Grimes, Thomas V. & Cundari, Thomas R., 1964-. 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, article, September 15, 2006; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc77187/: accessed December 14, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.