Measurement of heterogeneous reaction rates: three strategies for controlling mass transport and their application to indium-mediated allylations

J Phys Chem A. 2011 Oct 13;115(40):11001-7. doi: 10.1021/jp207383b. Epub 2011 Sep 20.

Abstract

We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Allyl Compounds / chemical synthesis*
  • Allyl Compounds / chemistry
  • Hydrocarbons, Halogenated / chemistry
  • Indium / chemistry*
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Particle Size
  • Photomicrography
  • Solutions
  • Stereoisomerism
  • Surface Properties

Substances

  • Allyl Compounds
  • Hydrocarbons, Halogenated
  • Organometallic Compounds
  • Solutions
  • Indium