Kinetic studies of ab initio investigations of the reactions of atomic bromine with methylsilane and dimethylsilane

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Article on kinetic studies and ab initio investigations of the reactions of atomic bromine with methylsilane and dimethylsilane.

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5 p.

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Ding, Luying & Marshall, Paul 1993.

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Article on kinetic studies and ab initio investigations of the reactions of atomic bromine with methylsilane and dimethylsilane.

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5 p.

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Abstract: The kinetics of the reactions of Br[4p(²Pᴊ)] with CH₃SiH₃ (1) and (CH₃)₂SiH₂ (2) have been measured using flash photolysis/time-resolved atomic resonance spectroscopy over the temperature ranges 350–550 and 390–550 K, respectively. The results are k₁=(4.0 ± 0.5) × 10⁻¹⁰ exp(–19.7 ± 0.5 kJ mol⁻¹/RT) and k₂ = (4.3 ± 0.8) × 10⁻¹⁰ exp(–21.6 ± 0.7 kJ mol⁻¹/RT) in units of cm³ s⁻¹, with confidence limits of ca. ± 13%. Assumed activation energies for the reverse reactions yield Si—H bond dissociation enthalpies, D₂₉₈, of 388 ± 5 and 392 ± 5 kJ mol⁻¹ in methylsilane and dimethylsilane, respectively. These values and the Arrhenius parameters are intermediate between earlier results for Br + SiH₄ and Br + (CH₃)₃SiH, although the uncertainty in D₂₉₈ is too great to establish a firm trend in D₂₉₈ with the degree of methylation. The silanes and corresponding silyl radicals are characterized by ab initio methods at up to the MP4/6-31G*//HF/6-31G* level.

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  • Journal of the Chemical Society, Faraday Transactions, 1993, Cambridge: Royal Society of Chemistry (Great Britain), pp. 419-423

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  • Publication Title: Journal of the Chemical Society, Faraday Transactions
  • Volume: 89
  • Issue: 3
  • Page Start: 419
  • Page End: 423
  • Pages: 5
  • Peer Reviewed: Yes

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  • 1993

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  • April 25, 2015, 8:59 p.m.

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Ding, Luying & Marshall, Paul. Kinetic studies of ab initio investigations of the reactions of atomic bromine with methylsilane and dimethylsilane, article, 1993; [Cambridge, England]. (digital.library.unt.edu/ark:/67531/metadc503246/: accessed October 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.