Gas-phase study of the formation and dissociation of Fe(CO)4H2: Kinetics and bond dissociation energies

Wenhua Wang; Amy A. Narducci; Paul G. House; Eric Weitz

doi:10.1021/ja960252t

Gas-phase study of the formation and dissociation of Fe(CO)₄H₂: Kinetics and bond dissociation energies

Wenhua Wang, Amy A. Narducci, Paul G. House, Eric Weitz^*

^*Corresponding author for this work

Chemistry

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36 Scopus citations

Abstract

Time-resolved IR spectroscopy has been used to study the oxidative addition of H₂ to Fe(CO)₄ and its reverse reaction, the reductive elimination of H₂ from Fe(CO)₄H₂, in the gas phase. The rate constant for oxidative addition of H₂ shows little temperature dependence, indicating that if there is an activation barrier for this process it is small (< 4 kcal mol^-1). The activation barrier for the reductive elimination of H₂ is 20.5 ± 2.1 kcal mol^-1. these measurements, the average of the dissociation energies for the two Fe-H bonds in Fe(CO)₄H₂ is calculated to be 62 ± 2 kcal mol^-1. Kinetic measurements employing D₂ indicate small kinetic isotope effects for both the oxidative addition and reductive elimination reactions.

Original language	English (US)
Pages (from-to)	8654-8657
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	118
Issue number	36
DOIs	https://doi.org/10.1021/ja960252t
State	Published - Sep 11 1996

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Gas-phase study of the formation and dissociation of Fe(CO)4H2: Kinetics and bond dissociation energies",

abstract = "Time-resolved IR spectroscopy has been used to study the oxidative addition of H2 to Fe(CO)4 and its reverse reaction, the reductive elimination of H2 from Fe(CO)4H2, in the gas phase. The rate constant for oxidative addition of H2 shows little temperature dependence, indicating that if there is an activation barrier for this process it is small (< 4 kcal mol-1). The activation barrier for the reductive elimination of H2 is 20.5 ± 2.1 kcal mol-1. these measurements, the average of the dissociation energies for the two Fe-H bonds in Fe(CO)4H2 is calculated to be 62 ± 2 kcal mol-1. Kinetic measurements employing D2 indicate small kinetic isotope effects for both the oxidative addition and reductive elimination reactions.",

author = "Wenhua Wang and Narducci, {Amy A.} and House, {Paul G.} and Eric Weitz",

year = "1996",

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T1 - Gas-phase study of the formation and dissociation of Fe(CO)4H2

T2 - Kinetics and bond dissociation energies

AU - Wang, Wenhua

AU - Narducci, Amy A.

AU - House, Paul G.

AU - Weitz, Eric

PY - 1996/9/11

Y1 - 1996/9/11

N2 - Time-resolved IR spectroscopy has been used to study the oxidative addition of H2 to Fe(CO)4 and its reverse reaction, the reductive elimination of H2 from Fe(CO)4H2, in the gas phase. The rate constant for oxidative addition of H2 shows little temperature dependence, indicating that if there is an activation barrier for this process it is small (< 4 kcal mol-1). The activation barrier for the reductive elimination of H2 is 20.5 ± 2.1 kcal mol-1. these measurements, the average of the dissociation energies for the two Fe-H bonds in Fe(CO)4H2 is calculated to be 62 ± 2 kcal mol-1. Kinetic measurements employing D2 indicate small kinetic isotope effects for both the oxidative addition and reductive elimination reactions.

AB - Time-resolved IR spectroscopy has been used to study the oxidative addition of H2 to Fe(CO)4 and its reverse reaction, the reductive elimination of H2 from Fe(CO)4H2, in the gas phase. The rate constant for oxidative addition of H2 shows little temperature dependence, indicating that if there is an activation barrier for this process it is small (< 4 kcal mol-1). The activation barrier for the reductive elimination of H2 is 20.5 ± 2.1 kcal mol-1. these measurements, the average of the dissociation energies for the two Fe-H bonds in Fe(CO)4H2 is calculated to be 62 ± 2 kcal mol-1. Kinetic measurements employing D2 indicate small kinetic isotope effects for both the oxidative addition and reductive elimination reactions.

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Gas-phase study of the formation and dissociation of Fe(CO)₄H₂: Kinetics and bond dissociation energies

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