Effects of alkyl chain structure on carbon-halogen bond dissociation and β-hydride elimination by alkyl halides on a Cu(100) surface

Jong Liang Lin, Andrew V. Teplyakov, Brian E. Bent

Research output: Contribution to journalArticlepeer-review

54 Citations (Scopus)

Abstract

The effects of alkyl chain structure on the rate of carbon-halogen bond scission in alkyl chlorides, bromides, and iodides on a Cu(100) surface and on the rates of β-hydride elimination by the alkyl products of these carbon-halogen bond scission reactions have been studied under ultra-high-vacuum conditions. It is found that the carbon-halogen bond dissociation rates increase in the order: C-Cl < C-Br < C-I and C(1°)-X < C(2°)-X < C(3°)-X, where X denotes the halogen and 1°, 2°, 3° refer to the number of alkyl substituents at the halogen-substituted carbon. β-Hydride elimination by the corresponding alkyl groups shows the following trends: (1) alkyl chain length (greater than three carbons) does not significantly affect the rate of β-hydride elimination; (2) the rate increases with alkyl substitution at the α-carbon in the order primary alkyls < secondary alkyls, (3) the rate of increase is substantially larger than expected on the basis of the increase in the number of β-hydrogens, and (4) for C5 and C6 alkyls the rate of this reaction is faster for 3-alkyls than for 2-alkyls. Differences in rate of up to 3 orders of magnitude are observed as a function of alkyl chain structure, and possible correlations between thermodynamic and kinetic effects are discussed.

Original languageEnglish
Pages (from-to)10721-10731
Number of pages11
JournalJournal of Physical Chemistry
Volume100
Issue number25
DOIs
Publication statusPublished - 1996 Jun 20

All Science Journal Classification (ASJC) codes

  • General Engineering
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'Effects of alkyl chain structure on carbon-halogen bond dissociation and β-hydride elimination by alkyl halides on a Cu(100) surface'. Together they form a unique fingerprint.

Cite this