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• W2040885989 abstract "A novel time-resolved CIDNP technique is used to measure absolute rate constants for the addition of 2-hydroxy-2-propyl radicals to 10 1,1- and two 1,2- disubstituted alkenes in propan-2-ol-d8 and toluene-d8 solvents and in part in acetonitrile-d3 and cyclohexane-d12, at room temperature. 2-Hydroxy-2-propyl radicals are produced by photolysis of 2,4-dihydroxy-2,4-dimethylpentan-3-one and lead to a multiplet effect CIDNP of the self-termination product, propan-2-ol, which follows a second-order termination kinetics. Addition of alkene partially quenches this polarization through the addition reaction. Quantitative measurement of the time-dependence and its simulation by kinetic equations yields the addition rate constant ka. The technique is applicable to systems with rate constants between 105 and 109 M-1 s-1, a range covered by the alkenes used. The data correlate with the alkene electron affinity and confirm the 2-hydroxy-2-propyl radical as very nucleophilic. A solvent dependence of ka up to 1 order magnitude is observed and is related to the hydrogen-bonding ability of the solvent and radical and to the polarity of the solvent. A β-steric effect of the alkene substituents is also noted." @default.
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• W2040885989 date "1996-01-01" @default.
• W2040885989 modified "2023-09-27" @default.
• W2040885989 title "Radical Addition Rates to Alkenes by Time-Resolved CIDNP: 2-Hydroxy-2-propyl Radicals" @default.
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• W2040885989 doi "https://doi.org/10.1021/jp9605109" @default.
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