Small Molecule Elimination from Group IVB (Ti, Zr, Hf) Amido Complexes

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This article discusses small molecule elimination from group IVB (Ti, Zr, Hf) amido complexes. An ab initio quantum chemical analysis of HX (X = H, CH₃, Cl, NH₂, SiH₃) elimination by group IVB (Ti, Zr, Hf) amidos (H₂(X)M - NH₂ → H₂M = NH + HX), of interest in the context of CVD precursor design, is reported.

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8 p.

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Cundari, Thomas R., 1964- & Gordon, Mark S. May 1993.

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This article discusses small molecule elimination from group IVB (Ti, Zr, Hf) amido complexes. An ab initio quantum chemical analysis of HX (X = H, CH₃, Cl, NH₂, SiH₃) elimination by group IVB (Ti, Zr, Hf) amidos (H₂(X)M - NH₂ → H₂M = NH + HX), of interest in the context of CVD precursor design, is reported.

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8 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 1993 American Chemical Society.

Abstract: An ab initio quantum chemical analysis of HX (X = H, CH₃, Cl, NH₂, SiH₃) elimination by group IVB (Ti, Zr, Hf) amidos (H₂(X)M - NH₂ → H₂M = NH + HX), of interest in the context of CVD precursor design, is reported. Several deductions may be drawn from the calculations. First, in the transition state (TS) for HX elimination, electropositive and electroneutral X give rise to metal-transannular hydrogen (Ht) distances only slightly longer than normal metal-terminal hydride bonds lengths, while electronegative X groups yield substantially longer MHt distances. Second, the HX elimination barrier (∆Hǂelim) is lower when HX is polarized Hδ- • Hδ+ (X = SiH₃) or nonpolar (X = H). Third, a plot of calculated ∆Hǂelim versus MHt distances in the TS. Fourth, analysis of the electronic structure along the intrinsic reaction coordinate (IRC) supports the importance of N-H•••M agostic interactions preceding N-H scission. Fifth, the IRC shows the MHt distance decreasing as Ht is transferred from N to X, reaching a minimum when the transfer is roughly half complete, and then increasing once more is HX is eliminated. These results point to the leaving group (X) playing a crucial role in tuning the bonding the energetics of the TS, and thus the rate of HX elimination. The results lead to the conclusion that materials precursors designed to enhance MHt interaction, through the intermediacy of X, in the TS and along the reaction coordinate will lead to lower activation barriers to XH elimination.

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  • Journal of the American Chemical Society, 1993, Washington DC: American Chemical Society, pp. 4210-4217

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 115
  • Issue: 10
  • Page Start: 4210
  • Page End: 4217
  • Peer Reviewed: Yes

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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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  • May 1993

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  • Oct. 9, 2012, 10:02 a.m.

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  • July 23, 2013, 11:48 a.m.

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Cundari, Thomas R., 1964- & Gordon, Mark S. Small Molecule Elimination from Group IVB (Ti, Zr, Hf) Amido Complexes, article, May 1993; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107776/: accessed April 29, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.