Combined Experimental and Computational Studies on the Nature of Aromatic C-H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies

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Article discussing combined experimental and computational studies on the nature of aromatic C-H activation by octahedral ruthenium(II) complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3].

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DeYonker, Nathan J.; Foley, Nicholas A.; Cundari, Thomas R., 1964-; Gunnoe, T. Brent & Petersen, Jeffrey L. November 27, 2007.

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Article discussing combined experimental and computational studies on the nature of aromatic C-H activation by octahedral ruthenium(II) complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3].

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8 p.

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Reprinted with permission from Organometallics. Copyright 2007 American Chemical Society.

Abstract: Octahedral ruthenium complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3] have been shown previously to initiate the C-H activation of aromatic substrates. In order to probe the nature of the C-H activation step, reaction rates have been theoretically obtained for the conversion of TpRu(L)(ƞ2-C,C-C6H5X)Me to TpRu(L)(ρ-C6H4X) and CH4 where X is varied among Br, Cl, CN, F, H, NH2, NO2, and OMe. A linear Hammett correlation is calculated with a positive ρ value of 2.6 for L = CO and 3.2 for L = PMe3. Calculated kinetic data for the aromatic C-H activations indicate that an electrophilic aromatic substitution mechanism is unlikely. While experiments cannot fully replicate the entire range of calculated Hammett plots, reactivity trends are consistent with the calculations that suggest activation barriers to overall metal-mediated arene C-H bond cleavage are reduced by the presence of electron-withdrawing groups in the position para to the site of activation. Previous mechanistic studies, as well as the structure and imaginary vibrational modes of the present transition states, validate that the C-H activation for this family of TpRu complexes occurs through a σ-bond metathesis-type pathway.

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  • Organometallics, 2007, Washington DC: American Chemical Society, pp. 6604-6611

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  • Publication Title: Organometallics
  • Volume: 26
  • Issue: 26
  • Page Start: 6604
  • Page End: 6611
  • Peer Reviewed: Yes

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  • November 27, 2007

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  • April 23, 2012, 10:02 a.m.

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  • May 12, 2014, 3:37 p.m.

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DeYonker, Nathan J.; Foley, Nicholas A.; Cundari, Thomas R., 1964-; Gunnoe, T. Brent & Petersen, Jeffrey L. Combined Experimental and Computational Studies on the Nature of Aromatic C-H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies, article, November 27, 2007; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc83332/: accessed February 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.