Reactions of Fe(CO) 4 with C 2H 5I in the gas phase: Evidence for the formation of IFe(CO) 4C 2H 5, IFe(CO) 3(η 2-COC 2H 5), and IFe(CO) 4(COC 2H 5)

David L. Cedeño; Eric Weitz

doi:10.1021/om0492348

Reactions of Fe(CO) ₄ with C ₂H ₅I in the gas phase: Evidence for the formation of IFe(CO) ₄C ₂H ₅, IFe(CO) ₃(η ²-COC ₂H ₅), and IFe(CO) ₄(COC ₂H ₅)

David L. Cedeño^*, Eric Weitz

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The reaction of C ₂H ₅I with photogenerated Fe(CO) ₄ was followed using time-resolved infrared spectroscopy. Three novel products were detected. On the basis of their carbonyl stretching frequencies, their kinetics, and calculations of their relative energies, these complexes are assigned as IFe(CO) ₄(C ₂H ₅), IFe(CO) ₃(η ²-COC ₂H ₅), and IFe(CO) ₄(COC ₂H ₅). Addition of C ₂H ₅I to Fe(CO) ₄ produces IFe(CO) ₄(C ₂H ₅) as the kinetically preferred product, which then converts to IFe(CO) ₃(η ²-COC ₂H ₅), the thermodynamically preferred complex. IFe(CO) ₄(COC ₂H ₅) is formed upon addition of CO to IFe(CO) ₃(η ¹-COC ₂H ₅), a 16-electron complex that is proposed as a common intermediate leading to the three products. Temperature-dependent studies of the kinetics of the decay of IFe(CO) ₄(COC ₂H ₅), the longest lived of the products, indicate that it decarbonylates with an activation energy of ∼20 kcal/mol.

Original language	English (US)
Pages (from-to)	1233-1241
Number of pages	9
Journal	Organometallics
Volume	24
Issue number	6
DOIs	https://doi.org/10.1021/om0492348
State	Published - Mar 14 2005

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Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Reactions of Fe(CO) 4 with C 2H 5I in the gas phase: Evidence for the formation of IFe(CO) 4C 2H 5, IFe(CO) 3(η 2-COC 2H 5), and IFe(CO) 4(COC 2H 5)",

abstract = "The reaction of C 2H 5I with photogenerated Fe(CO) 4 was followed using time-resolved infrared spectroscopy. Three novel products were detected. On the basis of their carbonyl stretching frequencies, their kinetics, and calculations of their relative energies, these complexes are assigned as IFe(CO) 4(C 2H 5), IFe(CO) 3(η 2-COC 2H 5), and IFe(CO) 4(COC 2H 5). Addition of C 2H 5I to Fe(CO) 4 produces IFe(CO) 4(C 2H 5) as the kinetically preferred product, which then converts to IFe(CO) 3(η 2-COC 2H 5), the thermodynamically preferred complex. IFe(CO) 4(COC 2H 5) is formed upon addition of CO to IFe(CO) 3(η 1-COC 2H 5), a 16-electron complex that is proposed as a common intermediate leading to the three products. Temperature-dependent studies of the kinetics of the decay of IFe(CO) 4(COC 2H 5), the longest lived of the products, indicate that it decarbonylates with an activation energy of ∼20 kcal/mol.",

author = "Cede{\~n}o, {David L.} and Eric Weitz",

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AU - Cedeño, David L.

AU - Weitz, Eric

PY - 2005/3/14

Y1 - 2005/3/14

N2 - The reaction of C 2H 5I with photogenerated Fe(CO) 4 was followed using time-resolved infrared spectroscopy. Three novel products were detected. On the basis of their carbonyl stretching frequencies, their kinetics, and calculations of their relative energies, these complexes are assigned as IFe(CO) 4(C 2H 5), IFe(CO) 3(η 2-COC 2H 5), and IFe(CO) 4(COC 2H 5). Addition of C 2H 5I to Fe(CO) 4 produces IFe(CO) 4(C 2H 5) as the kinetically preferred product, which then converts to IFe(CO) 3(η 2-COC 2H 5), the thermodynamically preferred complex. IFe(CO) 4(COC 2H 5) is formed upon addition of CO to IFe(CO) 3(η 1-COC 2H 5), a 16-electron complex that is proposed as a common intermediate leading to the three products. Temperature-dependent studies of the kinetics of the decay of IFe(CO) 4(COC 2H 5), the longest lived of the products, indicate that it decarbonylates with an activation energy of ∼20 kcal/mol.

AB - The reaction of C 2H 5I with photogenerated Fe(CO) 4 was followed using time-resolved infrared spectroscopy. Three novel products were detected. On the basis of their carbonyl stretching frequencies, their kinetics, and calculations of their relative energies, these complexes are assigned as IFe(CO) 4(C 2H 5), IFe(CO) 3(η 2-COC 2H 5), and IFe(CO) 4(COC 2H 5). Addition of C 2H 5I to Fe(CO) 4 produces IFe(CO) 4(C 2H 5) as the kinetically preferred product, which then converts to IFe(CO) 3(η 2-COC 2H 5), the thermodynamically preferred complex. IFe(CO) 4(COC 2H 5) is formed upon addition of CO to IFe(CO) 3(η 1-COC 2H 5), a 16-electron complex that is proposed as a common intermediate leading to the three products. Temperature-dependent studies of the kinetics of the decay of IFe(CO) 4(COC 2H 5), the longest lived of the products, indicate that it decarbonylates with an activation energy of ∼20 kcal/mol.

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Reactions of Fe(CO) ₄ with C ₂H ₅I in the gas phase: Evidence for the formation of IFe(CO) ₄C ₂H ₅, IFe(CO) ₃(η ²-COC ₂H ₅), and IFe(CO) ₄(COC ₂H ₅)

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