Kinetics of the formation and bond cleavage reactions of an alkyl-bridged dicobalt organocobaloxime

In acetate buffer media (pH 4.5-5.4 2− ) and temperature (T), but it decreases with an increase in [H + ] and the ionic strength (I). Analysis of the log A t versus time data (A is the absorbance of 1 at time t) reveals that overall the reaction follows a biphasic consecutive reaction path with rate constants k 1 and k 2 and the change of absorbance is equal to {a 1 exp(-k 1 t) + a 2 exp(-k 2 t)}, where k 1 > k 2 .

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“…This type of biphasic kinetic profile has been simply described by a two‐step consecutive reaction scheme as shown in Eq. (2)

\begin{matrix} true \\ right normalA \overset{k_{1}}{\to} normalB \overset{k_{2}}{\to} normalC \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

“…With the help of Eq. (3), one can extract the rate constants from the plot of log 10 ( A t – A ∞ ) versus time data . In our present case, the reaction was monitored at 700 nm and the absorbance value at infinite time at this wavelength can be supposed to be zero since Fig.…”

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Singh

Das

Banerjee

et al. 2015

Int J of Chemical Kinetics

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“…250 nm (yZ x 10^ cm"^ ) and 228 nm (~2 x 10^ cm"^ ) (24). The yellow BrCofdmgHjgtHgO) which eluted from the Sephadex column was Alkylcobaloximes are known to undergo a rapid and reversible equilibrium reaction with (26)(27)(28)(29)(30)(31). In the equilibrium, one of the two pairs of hydrogen-bonded 0-H -0 units is converted to two separate OH units.…”

Section: List Of Figuresmentioning

confidence: 99%

“…Values of typically lie in the range 1-4 for various alkyl and aryl R groups (26,28,30). A plausible mechanism which would account for the curvature of the plot of vs^.…”

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confidence: 99%

Kinetic studies of organocobalt compounds related to vitamin B12 coenzymes

Gjerde

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Miscellaneous reagents Methods Analyses and characterization Inorganic product analysis Organic product analysis Product analysis in the presence of [Co(NH.lcBr](C10.)p Rate determinations Flash photolysis RESULTS AND DISCUSSION Decomposition of CgHgCHfCH^iCofdmgHjgtOHg) in the Presence of Kinetics Inorganic products Organic products Determination of activation parameters Kinetics of Reaction of CofdmgHjgtOHg) with Decomposition of CgHgCHfCHgiCofdmgHjgfOHg) in the Presence of HgOg and Co(NH^)gBr^"*' Kinetics 52 Competition studies in the presence of H.O. 53 Competition studies in the presence of CofNHgigBr 59 Decomposition of CgHgCHfCHgiCofdmgHjgfOHg) with Cu^^ 62 iii Kinetics for the Reaction of CgH5CH(CH3)(dmgH)2(0H2) with Fe^ Decomposition of CgHgCHfCHgjCofdmgHigCOHg) in Neutral Solution Confirmation of the value of k. Decomposition in the presence of CofNHgjgBr Decomposition in the presence of oxygen Decomposition of CgHgCHtCHgiCofdmgHjgfOHg) in the Presence of Co (en) 3^"^ Kinetics Inorganic products Organic products CONCLUSIONS PART II. SINGLE-ELECTRON REDUCTION OF CHROMIUM(III) COMPLEXES BY VITAMIN INTRODUCTION EXPERIMENTAL Materials »12s Miscellaneous reagents Methods Analyses and characterization Kinetics RESULTS AND DISCUSSION Stoichiometry of Reaction Kinetics for the Reaction of Vitamin B," with (H«0)cCrX^* Complexes 94

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“…The pH dependence indicated in Figure I-5 can easily be explained considering the known protonation equilibrium of benzyl(aquo)cobaloxime.Alkylcobaloximes are known to undergo a rapid and reversible equilibrium reaction with(73)(74)(75)(76)(77)(78).In the equilibrium, one of the two hydrogen bound 0-H....0 moieties is converted to two separate OH groups.The equilibrium is symbolized as: the range 1-10 M ^ for various alkyl and aryl groups(67,73,75,77)• If both the protonated and unprotonated…”

mentioning

confidence: 99%

Kinetics and mechanisms of the reactions of aliphatic free radicals with organocobaloximes and fluoropentaamminecobalt(III) ion, and of iron(III) with methylrhodoxime

Mchatton

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Cobaloxlmes Organochromlurn reagents 19 Miscellaneous reagents Methods Analyses and characterizations 23 % Co analysis Product analyses Rate determinations DESIGN OF COMPETITION EXPERIMENTS •CH(CH^)0C2H^ Radical-CfCHgigOH Radical RESULTS 41 Reactions of the-CHfCHgïOCgHg Radical with Organocobaloximes 41 Benzyl(aquo)cobaloxime, PhCHgCofdmgHjgOHg 4l Other alkylcobaloxlmes, RCo(dmgH)_OH_ (R = CH,, CH"CH_, and Reactions of the "CfCH^jgOH Radical with Organocobaloximes 55 Benzyl(aquo)cobaloxime, PhCHgCofdmgHjgOHg 55 Other alkylcobaloxlmes, RCo(dmgH)_0H_ (R = CH,, CH«CH_, and 63 î i I Products of the Coupling Reactions Between Selected Free Radicals and Benzy1(aquo)cobaloxime 72 Preparation of a Large Sample of 2-Methyl-1-phenyl-2-propano1 79 Protonation Constant for Benzyl coba loxi me 80 DISCUSSION 84 Mechanistic Alternatives 86 Electron transfer mechanisms 88 Bimolecular homolytic substitution 89 Addition-elimination mechanisms 91 Fate of the 0-radicals from 2-propanol and ethanol 97 Conclusions 99 PART II. REDUCTION OF FLUORGPENTAAMMINECOBALT(III), CoCNHgigF^*, BY 2-HYDR0XY-2-PR0PYL AND a-ETHOXYETHYL RADICALS 100

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Kinetics of the formation and bond cleavage reactions of an alkyl-bridged dicobalt organocobaloxime

Cited by 17 publications

References 5 publications

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Kinetic studies of organocobalt compounds related to vitamin B12 coenzymes

Kinetics and mechanisms of the reactions of aliphatic free radicals with organocobaloximes and fluoropentaamminecobalt(III) ion, and of iron(III) with methylrhodoxime

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Kinetics of the formation and bond cleavage reactions of an alkyl-bridged dicobalt organocobaloxime

Cited by 17 publications

References 5 publications

Kinetics and Mechanism of Oxidation of S2O32− by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Kinetics and Mechanism of Oxidation of S2O32− by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Kinetic studies of organocobalt compounds related to vitamin B12 coenzymes

Kinetics and mechanisms of the reactions of aliphatic free radicals with organocobaloximes and fluoropentaamminecobalt(III) ion, and of iron(III) with methylrhodoxime

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Product

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Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex