Novel method for the chemical generation of aliphatic radicals and its application to the kinetics of reduction of cobalt(III)-amine complexes by 2-hydroxy-2-propyl radicals

Espenson, James H.; Shimura, Makoto; Bakač, Andreja

doi:10.1021/ic00137a003

Cited by 19 publications

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“…• R + S -> Products (11) This method has been successfully demonstrated by Espenson, et al (10) for the reduction of CofNH^)^^^ and [^(en)^^* in.strongly acidic solution by •C(CH2)20H radical. This method also appears to be applicable to the reduction of 2-iodopropane, Equation 12, by 'C(CHg)20H radical (29).…”

Section: Two Fundamentally Distinct Methods Of Competition Kinetics Havementioning

confidence: 97%

“…The first of these, applicable to situations where the substrate is 2+ unreactive toward Cr (aq) on the time scale of the homolysis reaction, 2+ involves the competition between a measured excess of Cr (aq) and the substrate for the radical in question. This situation is illustrated by Equations 10 and 11.CrR^* t Cr^+faq) + -R(10)…”

mentioning

confidence: 99%

“…The data obtained are summarized in Tables 1-8 and 1-9. A plot of the data obtained at l.OM and O.OIOM according to Equation 76 is represented inFigure Cofen)^^* in strongly acidic solution has been independently studied(10). The rate constant, kgg = 1.7 x 10^ M ^ s \ at l.OM ionic strength and 25.0°C has been shown to be independent of hydrogen ion concentration in the region pH O-3.…”

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confidence: 99%

“…In the case of (^^OjgCrCfCHgjgOH^*, its shorter lifetime in solution (15) necessitated injection of thermostatted mixtures of Co(NH2)gF^* and Cc^en)^^* into 5.00 cm quartz cells containing freshly prepared organochromium solution.The reaction was allowed to proceed for 60 seconds (greater than 10 halflives) and the fluoride ion content analyzed. Hydroxy-2-pro&yl radicalThe rate constant for reduction of Cc^NH^j^F^* by "CXCH^jgOH radical Ox was determined via competition with Cc^en)^ whose rate constant for reduction by "[(CH^jgOH radical is known(10). Homolysis of the CrCfCHgjgOH^* complex(15) in the presence of mixtures of Co(NH2)gF^* and Co(en)j^^, and the fate of the Cr^^(aq) and the organic radical produced are represented in Equations 100-103.…”

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confidence: 99%

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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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Section: Two Fundamentally Distinct Methods Of Competition Kinetics Havementioning

confidence: 97%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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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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“…2 .0(09^)208 > (CH^)2CH0H + (CH^)2C0 (1)(2)(3)(4)(5) Because this radical is subject to rapid self-reaction, direct kinetic determinations are limited to substrates which react with it quite rapidly. In practice, the techniques of radiation chemistry applied to aliphatic radicals are limited to reactions which have k > 3 x lO^M ^ (7).…”

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confidence: 99%

Kinetic and mechanistic studies of the reactions of selected aliphatic radicals with metal complexes and the decomposition of organoperoxy cobalt complexes

Chen

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The reaction of vanadixjm(II) with the 2-hydroxy-2propyl radical 23 Organic products 23 Inorganic product 25 The reaction of vanadium(II) with the 1-ethoxyethyl radical The reactions of (H2O)2Co^^([14]aneN^) with radicals 29 Organocobalt(III) intermediate 30 Kinetics 31 The reactions of vanadium(II) with radicals Primary deuterium isotope effect The reactions of (H2O) 2^0^^ ([ 14] aneN^) with radicals INTERPRETATION AND DISCUSSION Mechanisms of the Oxidation of Vanadium(II) Ion with Free Radicals Competitive kinetics The roles of radicals and vanadium(II) ion Reaction mechanisms Outer-sphere electron transfer 46 Hydrogen atom abstraction 47 V-C bond formation followed by acidolysis 48 Preequilibrium process 49 II 2+ Mechanisms of Reactions of Co ([14]aneN^) with Radicals 50 Inner-sphere mechanism 51 The pathway of the Co-C bond formation 51 The decomposition of the Co-C bond 52 Reactions of hydridocobalt complex 54 Outer-sphere electron transfer 54 CONCLUSIONS 57a iv PART II. REACTIONS OF (ALKYLPEROXY)COBALOXIMES IN ACIDIC AQUEOUS SOLUTIONS 58 Organic compounds 70 Cyclopentyl hydroperoxide 70 Miscellaneous reagents 71 Methods 71 Characterization of the synthesized compounds 71 Product identification 75 Kinetics 87 Spectrophotometry 87 Gas chromatography 91 RESULTS 93 Product Analysis 93 NMR analysis 93 lodometric titration 100 Kinetics 101

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Homolytic and Free Radical Pathways in the Reactions of Organochromium Complexes

Espenson

1983

Progress in Inorganic Chemistry

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Novel method for the chemical generation of aliphatic radicals and its application to the kinetics of reduction of cobalt(III)-amine complexes by 2-hydroxy-2-propyl radicals

Cited by 19 publications

References 0 publications

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

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

Kinetic and mechanistic studies of the reactions of selected aliphatic radicals with metal complexes and the decomposition of organoperoxy cobalt complexes

Homolytic and Free Radical Pathways in the Reactions of Organochromium Complexes

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