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- W2082122550 endingPage "1508" @default.
- W2082122550 startingPage "1498" @default.
- W2082122550 abstract "The reaction pathways (including the transition states) of ethylene addition to osmium tetroxide (OsO4, and amine ligated), rhenate (ReO4−), technetate (TcO4−), and permanganate (MnO4−) have been studied by qualitative and quantitative analyses. Distortion/interaction and absolutely localized energy decomposition analyses provide new insights into why the (3 + 2) pathway is highly preferred over the (2 + 2) pathway, the origin of rate enhancement from ligated base, and reactivity differences between OsO4, ReO4−, TcO4−, and MnO4−. The (2 + 2) transition state has a much larger barrier than the (3 + 2) transition state because (1) the Os−O bond is stretched significantly resulting in a larger distortion energy (ΔEd⧧) value and (2) the transition state interaction energy (ΔEi⧧) is destabilizing due to large exchange repulsions overwhelming stabilizing charge-transfer terms. Base ligation lowers osmium tetroxide and ethylene distortion energies due to the ground-state O−Os−O angle being predistorted from 110° to 103°. Because MO4 distortion energies are comparable, reactivity differences between OsO4, ReO4−, TcO4−, and MnO4− is shown to be a function of ethylene to MO4 charge-transfer. This interaction also dictates the position of the transition state along the reaction coordinate and corresponds to the onset of a stabilizing ΔEi⧧ value. The conceptual DFT hardness profile and hardness response show that the (3 + 2) reaction pathway may be classified as an “allowed” pathway while the (2 + 2) reaction coordinate is best designated as “forbidden”." @default.
- W2082122550 created "2016-06-24" @default.
- W2082122550 creator A5086726463 @default.
- W2082122550 date "2009-01-13" @default.
- W2082122550 modified "2023-10-12" @default.
- W2082122550 title "Distortion, Interaction, and Conceptual DFT Perspectives of MO<sub>4</sub>−Alkene (M = Os, Re, Tc, Mn) Cycloadditions" @default.
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