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• W2074098560 abstract "Abstract The thermodynamics of Ln(III) coordination of acrylate and propiolate (propynoate) have been investigated by potentiometry and calorimetry. The ΔS 101 values obtained have been used to evaluate the extent of outer-sphere complexation. For Ln = La, ΔS 101 = 61 and 34 J mol −1 K −1 for acrylate and propiolate, respectively, indicating 91% inner-sphere complexation for acrylate and 51% for propiolate. Gd(III)-induced 13 C relaxation rate enhancements have been applied to elucidate the geometries of the concerning complexes. Complexes of chloroacetates, of which the thermodynamics have been investigated previously, have been included in this study. The measurements on mono-, di- and trichloroacetate reveal an increasing extent of outer-sphere complexation with Gd(III) across the ligand series in aqueous solution. Monodentate coordination is an intermediate stage between bidentate and outer-sphere complexation. Coordination behavior analogous to the chloroacetates is observed for acrylate and propiolate. The extent of inner-sphere coordination determined in this way agrees well with the conclusions drawn from the formation entropy data. The obtained complex structures have been used to reevaluate previous 139 La NMR data." @default.
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• W2074098560 date "1996-04-01" @default.
• W2074098560 modified "2023-09-27" @default.
• W2074098560 title "Coordination of monocarboxylates in lanthanide(III) complexes" @default.
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• W2074098560 doi "https://doi.org/10.1016/0020-1693(95)04805-7" @default.
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