Activation of Carbon-Hydrogen and Hydrogen-Hydrogen Bonds by Copper-Nitrenes: A Comparison of Density Functionality Theory with Single- and Multireference Correlation Consistent Composite Approaches

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Article on a comparison of density functional theory with single- and multireference correlation consistent composite approaches (ccCA).

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8 p.

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Tekarli, Sammer M.; Williams, T. Gavin & Cundari, Thomas R., 1964- October 19, 2009.

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Article on a comparison of density functional theory with single- and multireference correlation consistent composite approaches (ccCA).

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8 p.

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Reprinted with permission from the Journal of Chemical Theory and Computation. Copyright 2009 American Chemical Society.

Abstract: The kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bonds (the former of methane) have been studied using several levels of theory: B3LYP/6-311++G(d,p), B97-1/cc-pVTZ, PBE1KCIS/cc-pVTZ, and ccCA (correlation consistent Composite Approach). The results show no significant difference among the DFT methods. All three DFT methods predict the ground state of the copper-nitrene model complex, L'Cu(NH), to be a triplet, while single reference ccCA predicts the singlet to be the ground state. The contributions to the total ccCA energy indicate that the singlet state is favored at the MP2/CBS level of theory, while electron correlation beyond this level (CCSD(T)) favors a triplet state, resulting in a close energetic balance between the two states. A multireference ccCA method is applied to the nitrene active species and supports the assignment of a singlet ground state. In general, the largest difference in the model reaction cycles between DFT and ccCA methods is for processes involving radicals and bond dissociation.

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  • Journal of Chemical Theory and Computation, 2009, Washington DC: American Chemical Society, pp. 2959-2966

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  • Publication Title: Journal of Chemical Theory and Computation
  • Volume: 5
  • Issue: 11
  • Page Start: 2959
  • Page End: 2966
  • Peer Reviewed: Yes

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  • October 19, 2009

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  • Oct. 9, 2012, 10:02 a.m.

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  • May 12, 2014, 11:27 a.m.

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Tekarli, Sammer M.; Williams, T. Gavin & Cundari, Thomas R., 1964-. Activation of Carbon-Hydrogen and Hydrogen-Hydrogen Bonds by Copper-Nitrenes: A Comparison of Density Functionality Theory with Single- and Multireference Correlation Consistent Composite Approaches, article, October 19, 2009; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc107767/: accessed September 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.