title: Light-enhanced displacement of methyl acrylate from iron carbonyl: investigation of the reactive intermediate via rapid-scan Fourier transform infrared and computational studies.
abstract: The thermal displacement of methyl acrylate from Fe(CO)4(η(2)-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 η(4) 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.
authors.affiliation: Department of Chemistry, Texas A&M University at Qatar , Doha, Qatar.
authors.forename: Sohail
authors.initials: S
authors.lastname: Muhammad
authors.forename: Salvador
authors.initials: S
authors.lastname: Moncho
authors.forename: Bo
authors.initials: B
authors.lastname: Li
authors.forename: Samuel J
authors.initials: SJ
authors.lastname: Kyran
authors.forename: Edward N
authors.initials: EN
authors.lastname: Brothers
authors.forename: Donald J
authors.initials: DJ
authors.lastname: Darensbourg
authors.forename: Ashfaq A
authors.initials: AA
authors.lastname: Bengali