Light-enhanced displacement of methyl acrylate from iron carbonyl: Investigation of the reactive intermediate via rapid-scan fourier transform infrared and computational studies

Sohail Muhammad, Salvador Moncho, Bo Li, Samuel J. Kyran, Edward N. Brothers, Donald J. Darensbourg, Ashfaq A. Bengali

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The thermal displacement of methyl acrylate from Fe(CO)42-CH2=CHCOOMe) by phosphine ligands is a relatively slow reaction requiring several hours at elevated temperatures. In the present study, it is observed that photolysis of the tetracarbonyl complex with UV light activates the process such that the reaction is complete within a few seconds. This rate enhancement is due to the formation of an intermediate η4 complex where the organic C=O and C=C units of methyl acrylate occupy axial and equatorial coordination sites on the Fe center, respectively, following photochemical CO loss. The displacement of methyl acrylate from this photolytically generated intermediate is facile with a remarkably low barrier of 8.7 kcal/mol. Density functional theory calculations support these experimental observations.

Original languageEnglish
Pages (from-to)12655-12660
Number of pages6
JournalInorganic Chemistry
Issue number21
Publication statusPublished - 4 Nov 2013


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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