Calculation of a Methane C-H Oxidative Addition Trajectory: Comparison to Experiment and Methane Activation by High-Valent Complexes

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Article discussing research on the calculation of methane C-H oxidative addition trajectory and a comparison to experiment and methane activation by high-valent complexes.

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8 p.

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Cundari, Thomas R., 1964- January 1994.

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Article discussing research on the calculation of methane C-H oxidative addition trajectory and a comparison to experiment and methane activation by high-valent complexes.

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8 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 1994 American Chemical Society.

Abstract: An effective core potential (ECP), parallel supercomputing study of methane activation by 14-electron, Ir(PH₃)₂(X) complexes (X = H, Cl) is presented. Considerable weakening of the coordinated methane C-H bond occurs upon formation of an ɳ²-CH coordinated (X)(PH₃)₂Ir•••HCH₃ adduct. A more strongly bound adduct (with greater weakening of the coordinated C-H bond) occurs when X = Cl versus X = H. The calculated Ir(PH₃)₂(H) + CH₄ → Ir(PH₃)₂(H)₂(Me) reaction enthalpy is -12.8 kcal mol⁻¹, and -41.6 kcal mol⁻¹ for the chloro analogue. The intrinsic reaction coordinate is calculated and compared to an experimental trajectory. Analysis of the wave function along the intrinsic reaction coordinate (IRC) suggests that although donation of electron density from methane to metal is essential for adduct formation, it is not until backdonation to σ* сʜ increases that the C-H bond is activated and cleaved. The electronic and molecular structure of the reacting system along the IRC suggest a two-stage mechanism: substrate to complex donation is important in the early part of the reaction (electrophilic stage) while complex to substrate backdonation is necessary later on (nucleophilic stage) for C-H scission. Finally, comparison of IRCs for low- and high-valent methane-activating complexes shows similar topology in the early portion of the activation event; differentiation between oxidative addition and σ-bond metathesis occurs at the point at which there is a shift from the electrophilic to nucleophilic stage of the reaction.

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  • Journal of the American Chemical Society, 1994, Washington DC: American Chemical Society, pp. 340-347

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 116
  • Issue: 1
  • Page Start: 340
  • Page End: 347
  • Peer Reviewed: Yes

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  • January 1994

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  • Oct. 9, 2012, 10:02 a.m.

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  • May 12, 2014, 2:10 p.m.

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Cundari, Thomas R., 1964-. Calculation of a Methane C-H Oxidative Addition Trajectory: Comparison to Experiment and Methane Activation by High-Valent Complexes, article, January 1994; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc107777/: accessed December 13, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.