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

Ann Mueting; B. M. Mattson

doi:10.1016/0022-1902(81)80215-1

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

Ann Mueting, B. M. Mattson

Department of Chemistry

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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, K^χ = [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 language	English (US)
Pages (from-to)	749-751
Number of pages	3
Journal	Journal of Inorganic and Nuclear Chemistry
Volume	43
Issue number	4
DOIs	https://doi.org/10.1016/0022-1902(81)80215-1
State	Published - 1981

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@article{d6e6a995641e4a0abc0e6e97ac7cb77e,

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).",

author = "Ann Mueting and Mattson, {B. M.}",

note = "Funding Information: Acknowledgements--We wish to acknowledge financial support by a Cottrell Science Grant from Research Corporation and a Graduate School Grant from Creighton University. We also wish to acknowledge helpful discv~sions with Dr. D. M. Zebolsky.",

year = "1981",

doi = "10.1016/0022-1902(81)80215-1",

language = "English (US)",

volume = "43",

pages = "749--751",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "4",

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T1 - Kinetics and thermodynamics of the intramolecular isomerization of [Fe(SCH3(CO)3]4

AU - Mueting, Ann

AU - Mattson, B. M.

N1 - Funding Information: Acknowledgements--We wish to acknowledge financial support by a Cottrell Science Grant from Research Corporation and a Graduate School Grant from Creighton University. We also wish to acknowledge helpful discv~sions with Dr. D. M. Zebolsky.

PY - 1981

Y1 - 1981

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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U2 - 10.1016/0022-1902(81)80215-1

DO - 10.1016/0022-1902(81)80215-1

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EP - 751

JO - Polyhedron

JF - Polyhedron

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ER -

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

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