A study of the kinetics of reaction of Fe(CO)3 and Fe(CO)3(L) with H2 and C2H4 for L = H2 and C2H4 by transient infrared spectroscopy: Reactions relevant to olefin hydrogenation kinetics

David M. Hayes; Eric Weitz

doi:10.1021/j100160a020

A study of the kinetics of reaction of Fe(CO)₃ and Fe(CO)₃(L) with H₂ and C₂H₄ for L = H₂ and C₂H₄ by transient infrared spectroscopy: Reactions relevant to olefin hydrogenation kinetics

David M. Hayes^*, Eric Weitz

^*Corresponding author for this work

Chemistry

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

26 Scopus citations

Abstract

The reactions of Fe(CO)₃ with ethylene and H₂ have been studied and rate constants for the formation of the H₂Fe(CO)₃ and Fe(CO)₃(ethylene) complexes have been obtained. Further reactions of these unsaturated products with ethylene and H₂ respectively have been shown to lead to formation of the H₂Fe(CO)₃(ethylene) complex which is a crucial intermediate in the proposed mechanism for Fe(CO)₃-induced hydrogenation of ethylene. The rate constants for formation of this complex from both precursors have been obtained and are reported along with the other rate constants determined in this study. Interestingly, though ethane is produced on a long time scale under the experimental conditions, H₂Fe(CO)₃(ethylene) is stable at room temperature in the approximately 100-μs observation time of these experiments. Significant differences have been observed for the rate constants of formation of the various complexes that were studied. These variations are discussed with respect to spin allowed versus disallowed reactions and the nature of the reacting ligand.

Original language	English (US)
Pages (from-to)	2723-2727
Number of pages	5
Journal	Journal of physical chemistry
Volume	95
Issue number	7
DOIs	https://doi.org/10.1021/j100160a020
State	Published - 1991

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General Engineering
Physical and Theoretical Chemistry

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title = "A study of the kinetics of reaction of Fe(CO)3 and Fe(CO)3(L) with H2 and C2H4 for L = H2 and C2H4 by transient infrared spectroscopy: Reactions relevant to olefin hydrogenation kinetics",

abstract = "The reactions of Fe(CO)3 with ethylene and H2 have been studied and rate constants for the formation of the H2Fe(CO)3 and Fe(CO)3(ethylene) complexes have been obtained. Further reactions of these unsaturated products with ethylene and H2 respectively have been shown to lead to formation of the H2Fe(CO)3(ethylene) complex which is a crucial intermediate in the proposed mechanism for Fe(CO)3-induced hydrogenation of ethylene. The rate constants for formation of this complex from both precursors have been obtained and are reported along with the other rate constants determined in this study. Interestingly, though ethane is produced on a long time scale under the experimental conditions, H2Fe(CO)3(ethylene) is stable at room temperature in the approximately 100-μs observation time of these experiments. Significant differences have been observed for the rate constants of formation of the various complexes that were studied. These variations are discussed with respect to spin allowed versus disallowed reactions and the nature of the reacting ligand.",

author = "Hayes, {David M.} and Eric Weitz",

year = "1991",

doi = "10.1021/j100160a020",

language = "English (US)",

volume = "95",

pages = "2723--2727",

journal = "Journal of physical chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - A study of the kinetics of reaction of Fe(CO)3 and Fe(CO)3(L) with H2 and C2H4 for L = H2 and C2H4 by transient infrared spectroscopy

T2 - Reactions relevant to olefin hydrogenation kinetics

AU - Hayes, David M.

AU - Weitz, Eric

PY - 1991

Y1 - 1991

N2 - The reactions of Fe(CO)3 with ethylene and H2 have been studied and rate constants for the formation of the H2Fe(CO)3 and Fe(CO)3(ethylene) complexes have been obtained. Further reactions of these unsaturated products with ethylene and H2 respectively have been shown to lead to formation of the H2Fe(CO)3(ethylene) complex which is a crucial intermediate in the proposed mechanism for Fe(CO)3-induced hydrogenation of ethylene. The rate constants for formation of this complex from both precursors have been obtained and are reported along with the other rate constants determined in this study. Interestingly, though ethane is produced on a long time scale under the experimental conditions, H2Fe(CO)3(ethylene) is stable at room temperature in the approximately 100-μs observation time of these experiments. Significant differences have been observed for the rate constants of formation of the various complexes that were studied. These variations are discussed with respect to spin allowed versus disallowed reactions and the nature of the reacting ligand.

AB - The reactions of Fe(CO)3 with ethylene and H2 have been studied and rate constants for the formation of the H2Fe(CO)3 and Fe(CO)3(ethylene) complexes have been obtained. Further reactions of these unsaturated products with ethylene and H2 respectively have been shown to lead to formation of the H2Fe(CO)3(ethylene) complex which is a crucial intermediate in the proposed mechanism for Fe(CO)3-induced hydrogenation of ethylene. The rate constants for formation of this complex from both precursors have been obtained and are reported along with the other rate constants determined in this study. Interestingly, though ethane is produced on a long time scale under the experimental conditions, H2Fe(CO)3(ethylene) is stable at room temperature in the approximately 100-μs observation time of these experiments. Significant differences have been observed for the rate constants of formation of the various complexes that were studied. These variations are discussed with respect to spin allowed versus disallowed reactions and the nature of the reacting ligand.

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U2 - 10.1021/j100160a020

DO - 10.1021/j100160a020

M3 - Article

AN - SCOPUS:0000114126

SN - 0022-3654

VL - 95

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EP - 2727

JO - Journal of physical chemistry

JF - Journal of physical chemistry

IS - 7

ER -

A study of the kinetics of reaction of Fe(CO)₃ and Fe(CO)₃(L) with H₂ and C₂H₄ for L = H₂ and C₂H₄ by transient infrared spectroscopy: Reactions relevant to olefin hydrogenation kinetics

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