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- W1988013184 abstract "Hydrolysis of Co(NO2)4(AA)− (AA=en or tn) was studied in acidic and basic aqueous solutions by the spectrophotometric method. In faintly acidic solution (6>pH>4) the aquation proceeds reversibly to attain an equilibrium with Co(NO2)3(H2O) (AA), Keq being (1.71±0.03)×10−2 and (3.55±0.06)×10−2 mol·1−1 for AA=en and tn, respectively, at 25.0 °C and μ=0.1. With increasing concentration of hydrogen ion the acid-catalyzed pathway becomes increasingly important. In basic solution (12.2>pH>9.5) Co(NO2)3(OH)(AA)− was formed irreversibly as the first product. Kinetic data of these hydrolysis reactions are interpreted in terms of the dissociative mechanism involving a five-coordinate intermediate Co(NO2)3(AA). The rates of nitrite release from Co(NO2)4(tn)− ((9.27±0.03)×10−4s−1) and deaquation from Co(NO2)3(H2O)(tn) ((3.95±0.12)×10−4 s−1) are several times greater than those for the corresponding ethylenediamine complexes ((2.08±0.01)×10−4 and (5.46±0.10)×10−5 s−1, respectively." @default.
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- W1988013184 date "1978-04-01" @default.
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- W1988013184 title "Trimethylenediamine Complexes. IV. Kinetics and Mechanism of Acid and Base Hydrolysis of Tetranitro(ethylenediamine)- and Tetranitro(trimethylenediamine)cobaltates(III)" @default.
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- W1988013184 doi "https://doi.org/10.1246/bcsj.51.1083" @default.
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