Light-enhanced displacement of methyl acrylate from iron carbonyl

Investigation of the reactive intermediate via rapid-scan fourier transform infrared and computational studies

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

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

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
Volume52
Issue number21
DOIs
Publication statusPublished - 4 Nov 2013

Fingerprint

Fourier Analysis
acrylates
Fourier transforms
phosphine
Iron
Carbon Monoxide
Infrared radiation
Light
iron
Photolysis
Ultraviolet Rays
phosphines
Ultraviolet radiation
Density functional theory
photolysis
Hot Temperature
density functional theory
Ligands
ligands
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

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; Moncho Escriva, Salvador; Li, Bo; Kyran, Samuel J.; Brothers, Edward; Darensbourg, Donald J.; Bengali, Ashfaq A.

In: Inorganic Chemistry, Vol. 52, No. 21, 04.11.2013, p. 12655-12660.

Research output: Contribution to journalArticle

@article{f3536dba6da24f9eb9e6a23afa717845,
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 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.",
author = "Muhammad Sohail and {Moncho Escriva}, Salvador and Bo Li and Kyran, {Samuel J.} and Edward Brothers and Darensbourg, {Donald J.} and Bengali, {Ashfaq A.}",
year = "2013",
month = "11",
day = "4",
doi = "10.1021/ic401836n",
language = "English",
volume = "52",
pages = "12655--12660",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Light-enhanced displacement of methyl acrylate from iron carbonyl

T2 - Investigation of the reactive intermediate via rapid-scan fourier transform infrared and computational studies

AU - Sohail, Muhammad

AU - Moncho Escriva, Salvador

AU - Li, Bo

AU - Kyran, Samuel J.

AU - Brothers, Edward

AU - Darensbourg, Donald J.

AU - Bengali, Ashfaq A.

PY - 2013/11/4

Y1 - 2013/11/4

N2 - 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 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.

AB - 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 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.

UR - http://www.scopus.com/inward/record.url?scp=84887057641&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887057641&partnerID=8YFLogxK

U2 - 10.1021/ic401836n

DO - 10.1021/ic401836n

M3 - Article

VL - 52

SP - 12655

EP - 12660

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -