Aliphatic radicals as reducing agents of cobalt(III) and ruthenium(III) complexes: A pulse radiolytic study

Haim Cohen; Dan Meyerstein

doi:10.1039/DT9770001056

Aliphatic radicals as reducing agents of cobalt(III) and ruthenium(III) complexes: A pulse radiolytic study

Haim Cohen, Dan Meyerstein

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Abstract

The pH effect on the rate of the reduction reaction ĊH₂OH + [Co(NH₃)₆]³⁺ has been studied. The results indicate that this reaction does not proceed via the outer-sphere mechanism. The pH effect on the reactivity of R¹Ċ(OH)CO₂H [R¹ = H,CH₃, or HO₂CCH(OH)] towards [Co(NH₃)₆]³⁺ and [Ru(NH₃)₆]³⁺ has been studied. The results indicate that the radicals R¹Ċ(OH)CO₂^- are considerably more reactive than R¹Ċ(OH)CO₂H. The reasons for this effect are discussed. The rate of water loss from the radical derived from tartaric acid has been measured. The kinetics of reduction of [CoX(NH₃)₅]²⁺ and [RuX(NH₃)₅]³⁺,(X = halide) and [Co^III(en)₂XY] (en = ethylenediamine; X,Y = F, Cl, Br, NH₃, or H₂O) by the radicals ĊH₂OH, MeĊHOH. Me₂ĊOH, Me₂ĊHOEt, and O-ĊH-CH₂-O-CH₂-CH₂ have been examined mechanism. The results suggest that these reactions proceed via a bridged mechanism.

Original language	English
Pages (from-to)	1056-1062
Number of pages	7
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	11
DOIs	https://doi.org/10.1039/DT9770001056
State	Published - 1 Dec 1977
Externally published	Yes

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General Chemistry

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title = "Aliphatic radicals as reducing agents of cobalt(III) and ruthenium(III) complexes: A pulse radiolytic study",

abstract = "The pH effect on the rate of the reduction reaction ĊH2OH + [Co(NH3)6]3+ has been studied. The results indicate that this reaction does not proceed via the outer-sphere mechanism. The pH effect on the reactivity of R1Ċ(OH)CO2H [R1 = H,CH3, or HO2CCH(OH)] towards [Co(NH3)6]3+ and [Ru(NH3)6]3+ has been studied. The results indicate that the radicals R1Ċ(OH)CO2- are considerably more reactive than R1Ċ(OH)CO2H. The reasons for this effect are discussed. The rate of water loss from the radical derived from tartaric acid has been measured. The kinetics of reduction of [CoX(NH3)5]2+ and [RuX(NH3)5]3+,(X = halide) and [CoIII(en)2XY] (en = ethylenediamine; X,Y = F, Cl, Br, NH3, or H2O) by the radicals ĊH2OH, MeĊHOH. Me2ĊOH, Me2ĊHOEt, and O-ĊH-CH2-O-CH2-CH2 have been examined mechanism. The results suggest that these reactions proceed via a bridged mechanism.",

author = "Haim Cohen and Dan Meyerstein",

year = "1977",

month = dec,

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doi = "10.1039/DT9770001056",

language = "English",

pages = "1056--1062",

journal = "Journal of the Chemical Society. Dalton Transactions",

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publisher = "Royal Society of Chemistry",

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T1 - Aliphatic radicals as reducing agents of cobalt(III) and ruthenium(III) complexes

T2 - A pulse radiolytic study

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1977/12/1

Y1 - 1977/12/1

N2 - The pH effect on the rate of the reduction reaction ĊH2OH + [Co(NH3)6]3+ has been studied. The results indicate that this reaction does not proceed via the outer-sphere mechanism. The pH effect on the reactivity of R1Ċ(OH)CO2H [R1 = H,CH3, or HO2CCH(OH)] towards [Co(NH3)6]3+ and [Ru(NH3)6]3+ has been studied. The results indicate that the radicals R1Ċ(OH)CO2- are considerably more reactive than R1Ċ(OH)CO2H. The reasons for this effect are discussed. The rate of water loss from the radical derived from tartaric acid has been measured. The kinetics of reduction of [CoX(NH3)5]2+ and [RuX(NH3)5]3+,(X = halide) and [CoIII(en)2XY] (en = ethylenediamine; X,Y = F, Cl, Br, NH3, or H2O) by the radicals ĊH2OH, MeĊHOH. Me2ĊOH, Me2ĊHOEt, and O-ĊH-CH2-O-CH2-CH2 have been examined mechanism. The results suggest that these reactions proceed via a bridged mechanism.

AB - The pH effect on the rate of the reduction reaction ĊH2OH + [Co(NH3)6]3+ has been studied. The results indicate that this reaction does not proceed via the outer-sphere mechanism. The pH effect on the reactivity of R1Ċ(OH)CO2H [R1 = H,CH3, or HO2CCH(OH)] towards [Co(NH3)6]3+ and [Ru(NH3)6]3+ has been studied. The results indicate that the radicals R1Ċ(OH)CO2- are considerably more reactive than R1Ċ(OH)CO2H. The reasons for this effect are discussed. The rate of water loss from the radical derived from tartaric acid has been measured. The kinetics of reduction of [CoX(NH3)5]2+ and [RuX(NH3)5]3+,(X = halide) and [CoIII(en)2XY] (en = ethylenediamine; X,Y = F, Cl, Br, NH3, or H2O) by the radicals ĊH2OH, MeĊHOH. Me2ĊOH, Me2ĊHOEt, and O-ĊH-CH2-O-CH2-CH2 have been examined mechanism. The results suggest that these reactions proceed via a bridged mechanism.

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Aliphatic radicals as reducing agents of cobalt(III) and ruthenium(III) complexes: A pulse radiolytic study

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