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Methane Activation by Group IVB Imido Complexes

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Article discussing an ab initio study of methane activation by group IVB imido complexes.

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7 p.

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Cundari, Thomas R., 1964- 1992.

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Article discussing an ab initio study of methane activation by group IVB imido complexes.

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7 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 1992 American Chemical Society.

Abstract: An ab initio study of methane activation by group IVB imido complexes, when coupled with available experimental data, reveals an interesting picture of this important reaction. Initial interaction of methane and (H)₂M=NH leads to the formation of alkane complexes bound by ≈9 kcal mol⁻¹. Experiment indicates that the polarity of the metal-ligand bond upon which the C-H is activated plays an important role in facilitating subsequent scission. Calculations support this hypothesis and suggest that formation of the alkane complex acts to increase Cδ-Hδ polarization, setting the stage for C-H cleavage. Calculated methane elimination barriers for (H)₂M(CH₃)(NH₂) (M=Ti, Zr, Hf) are in good agreement with experimental models in terms of absolute numbers and trends as a function of metal. Calculated methane activation barriers follow the order Ti > Zr > Hf, in line with calculated exothermicities. Calculated geometries indicate a late transition state for methane elimination, in agreement with experimentally determined activation parameters. The TSs have a kite-shaped geometry with an obtuse angle about the H of the C-H bond being activated (Ht) and a short MHt distance, 1-2% greater than normal. The short MHt distance suggests a stabilizing interaction, supported by a positive bond overlap population. Calculation of the intrinsic reaction coordinate demonstrates the importance of agostic interactions between N-H and M along the reaction coordinate.

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  • Journal of the American Chemical Society, 1992, Washington D.C.: American Chemical Society, pp. 10557-10563

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 114
  • Issue: 26
  • Page Start: 10557
  • Page End: 10563
  • Peer Reviewed: Yes

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UNT Scholarly Works

The Scholarly Works Collection is home to materials from the University of North Texas community's research, creative, and scholarly activities and serves as UNT's Open Access Repository. It brings together articles, papers, artwork, music, research data, reports, presentations, and other scholarly and creative products representing the expertise in our university community.** Access to some items in this collection may be restricted.**

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  • 1992

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  • Oct. 9, 2012, 10:02 a.m.

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  • Jan. 9, 2015, 5:08 p.m.

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Cundari, Thomas R., 1964-. Methane Activation by Group IVB Imido Complexes, article, 1992; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107807/: accessed March 30, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.