Kinetics and thermodynamics of the intramolecular isomerization of [Fe(SCH3(CO)3]4

Ann Mueting, Bruce M. Mattson

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Abstract

The kinetics and thermodynamics of the isomerization of syn- and anti-[Fe(SCH3)(CO3)]2 were investigated over the temperature range 40-70°C in chloroform and other solvents. In chloroform the thermodynamic parameters for the isomerization syn → anti are ΔH = 1.4 ± 1.1 kcal/mol, ΔS = 6.0 ± 2.6 cal/mol°K, ΔG298 = -0.4 ± 1.9 kcal/mol. The kinetic parameters for the same reaction are ΔH‡ = 28.4 ± 1.4 kcal/mol, ΔS‡ = 27.9 ± 4.2 cal/mol°K, and ΔG‡298 = 21.1 ± 2.6 kcal/mol. The isomerization is first order in both direction and probably involves FeS bond rupture and reformation. The equilibrium constant, Kχ = [anti]/[syn] varies from 1.89 ± 0.22 at 40°C to 2.26 ± 0.18 at 70°C. The rate of isomerization increases with solvent polarity hexane <toluene <CH3CN <CHCl3).

Original languageEnglish
Pages (from-to)749-751
Number of pages3
JournalJournal of Inorganic and Nuclear Chemistry
Volume43
Issue number4
DOIs
StatePublished - 1981

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Carbon Monoxide
Isomerization
isomerization
Thermodynamics
thermodynamics
Kinetics
kinetics
Chloroform
Chlorine compounds
chloroform
Equilibrium constants
Toluene
Hexanes
Hexane
Kinetic parameters
toluene
polarity
Temperature
temperature

Cite this

Kinetics and thermodynamics of the intramolecular isomerization of [Fe(SCH3(CO)3]4 . / Mueting, Ann; Mattson, Bruce M.

In: Journal of Inorganic and Nuclear Chemistry, Vol. 43, No. 4, 1981, p. 749-751.

Research output: Contribution to journalArticle

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title = "Kinetics and thermodynamics of the intramolecular isomerization of [Fe(SCH3(CO)3]4",
abstract = "The kinetics and thermodynamics of the isomerization of syn- and anti-[Fe(SCH3)(CO3)]2 were investigated over the temperature range 40-70°C in chloroform and other solvents. In chloroform the thermodynamic parameters for the isomerization syn → anti are ΔH = 1.4 ± 1.1 kcal/mol, ΔS = 6.0 ± 2.6 cal/mol°K, ΔG298 = -0.4 ± 1.9 kcal/mol. The kinetic parameters for the same reaction are ΔH‡ = 28.4 ± 1.4 kcal/mol, ΔS‡ = 27.9 ± 4.2 cal/mol°K, and ΔG‡298 = 21.1 ± 2.6 kcal/mol. The isomerization is first order in both direction and probably involves FeS bond rupture and reformation. The equilibrium constant, Kχ = [anti]/[syn] varies from 1.89 ± 0.22 at 40°C to 2.26 ± 0.18 at 70°C. The rate of isomerization increases with solvent polarity hexane 3CN <CHCl3).",
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AU - Mueting, Ann

AU - Mattson, Bruce M.

PY - 1981

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N2 - The kinetics and thermodynamics of the isomerization of syn- and anti-[Fe(SCH3)(CO3)]2 were investigated over the temperature range 40-70°C in chloroform and other solvents. In chloroform the thermodynamic parameters for the isomerization syn → anti are ΔH = 1.4 ± 1.1 kcal/mol, ΔS = 6.0 ± 2.6 cal/mol°K, ΔG298 = -0.4 ± 1.9 kcal/mol. The kinetic parameters for the same reaction are ΔH‡ = 28.4 ± 1.4 kcal/mol, ΔS‡ = 27.9 ± 4.2 cal/mol°K, and ΔG‡298 = 21.1 ± 2.6 kcal/mol. The isomerization is first order in both direction and probably involves FeS bond rupture and reformation. The equilibrium constant, Kχ = [anti]/[syn] varies from 1.89 ± 0.22 at 40°C to 2.26 ± 0.18 at 70°C. The rate of isomerization increases with solvent polarity hexane 3CN <CHCl3).

AB - The kinetics and thermodynamics of the isomerization of syn- and anti-[Fe(SCH3)(CO3)]2 were investigated over the temperature range 40-70°C in chloroform and other solvents. In chloroform the thermodynamic parameters for the isomerization syn → anti are ΔH = 1.4 ± 1.1 kcal/mol, ΔS = 6.0 ± 2.6 cal/mol°K, ΔG298 = -0.4 ± 1.9 kcal/mol. The kinetic parameters for the same reaction are ΔH‡ = 28.4 ± 1.4 kcal/mol, ΔS‡ = 27.9 ± 4.2 cal/mol°K, and ΔG‡298 = 21.1 ± 2.6 kcal/mol. The isomerization is first order in both direction and probably involves FeS bond rupture and reformation. The equilibrium constant, Kχ = [anti]/[syn] varies from 1.89 ± 0.22 at 40°C to 2.26 ± 0.18 at 70°C. The rate of isomerization increases with solvent polarity hexane 3CN <CHCl3).

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