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- W2949954965 abstract "The first-order rate constants (kY) at several temperatures in CDCl3 were measured for thermal decompositions of YC6H4CH2CO3C(CH3)3 with Y being p-OCH3, p-OPh, p-CH3, p-Ph, p-H, p-Cl, m-Cl, and p-NO2. The relative rates (kY/kH) exhibit excellent ρ+/σ+ Hammett correlations with ρ+ < 0, indicating a polar TS. Activation parameters (ΔH⧧Y and ΔS⧧Y) and their differential terms (ΔΔH⧧Y-H and ΔΔS⧧Y-H) were obtained from the Eyring plot. Differential activation terms (ΔΔH⧧Y-H and ΔΔS⧧Y-H) disclose an isokinetic relation with p-CH3, p-Ph, p-H, p-Cl, and m-Cl (isokinetic temp, 230 K). However, p-OCH3, and p-OPh show negative deviations, and a positive deviation occurs with p-NO2. Plot of ΔΔH⧧Y-H vs σ+ exhibits a good linear relation (r = 0.95) with a slope (α1 = −3.34). A better linear correlation (r = 0.97) and steeper slope (α2 = −5.22) were observed for TΔΔS⧧Y-H vs σ+. Negatively larger slope (α2 = −5.22) may point to entropy control of rates. Differential activation parameters (ΔΔH⧧Y-H and ΔΔS⧧Y-H) reflect variations of activation process. Differential activation entropies (ΔΔS⧧Y-H) are discussed in terms of contributions of translational and rotational entropies. Similar deviation behaviors of p-OCH3, p-OPh, and p-NO2 were again observed for the both plots. p-NO2 can strongly destabilize the cationic site of the polar TS but serves an eminent spin delocalizer for the homolytic TS." @default.
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- W2949954965 date "2001-05-02" @default.
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- W2949954965 title "Thermolysis of <i>tert</i>-Butyl Phenylperacetates: Delicate Control of the Rates through Contributions from Translational and Rotational Entropy" @default.
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