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- W2088298961 abstract "The kinetics of the addition of 4-formylpyridine to the coordinated dienyl ligand in tricarbonyl(1–5-η-dienyl)iron(II) complexes (1; dienyl = C6H7, 2-MeOC6H6 and C7H9) has been studied as a function of temperature and pressure in acetonitrile by stopped-flow techniqu The observed rate law is kobs = k1 [amine] + k−1, and low ΔH1ν values, large negative ΔS1ν and negati ΔV1ν values indicate that there is direct addition (k1) to the dienyl rings of complexes 1. On the other hand, the relatively higher ΔH−1ν values and positive ΔS−1ν values are as expected for bond cleavage (k−1), as are the positive ΔV−1 values determined for the dissociation of 4-formylpyridine from 1 (dienyl = C6H7 and 2-MeOC6H6). The large negative ΔS−1ν value of −150 ± 7 J K−1 mol−1 found for the dissociation of 4-formylpyridine from 1 (dienyl = C7H9) is consistent with the insensitivity of this reaction to pressure changes and so with operation of the previously suggested interchange/“ordered transition state” mechanism. A plot of ΔH−1ν versus ΔS−1ν yields an isokinetic temperature of 260±3 K, indicating entropy control in the dissociative process." @default.
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- W2088298961 date "1992-10-01" @default.
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- W2088298961 title "Significance of entropies and volumes of activation for the addition of 4-formylpyridine to tricarbonyl(1–5-η-dienyl)iron(II) complexes (dienyl = C6H7, 2-MeOC6H6 and C7H9)" @default.
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- W2088298961 doi "https://doi.org/10.1016/0022-328x(92)88012-8" @default.
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