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- W1978359982 abstract "Properties indirectly determined, or alluded to, in previous publications on the titled isomers have been measured, and the results generally support the earlier conclusions. Thus, the common five-coordinate intermediate generated in the OH−-catalyzed hydrolysis of exo- and endo-[Co(dien)(dapo)X]2+ (X=Cl, ONO2) has the same properties as that generated in the rapid spontaneous loss of OH− from exo- and endo-[Co(dien)(dapo)OH]2+ (40±2% endo-OH, 60±2% exo-OH) and an unusually large capacity for capturing (R=[CoN3]/[CoOH][]=1.3; exo-[CoN3]/endo-[CoN3]=2.1±0.1). Solvent exchange for spontaneous loss of OH− from exo-[Co(dien)(dapo)OH]2+ has been measured at 0.04 s−1 (k1, 0.50M NaClO4, 25°) from which similar loss from the endo-OH isomer may be calculated as 0.24 s−1 (k2). The OH−-catalyzed reactions of exo- and endo-[Co(dien)(dapo)N3]2+ result in both hydrolysis of coordinated via an OH−-limiting process =153 M−1 s−1; =295 M−1 s−1; KH=1.3±0.1 M−1; 0.50M NaClO4, 25.0°) and direct epimerization between the two reactants =33 M−1 s−1; =110 M−1 s−1; 1.0M NaClO4, 25.0°). Comparisons are made with other rapidly reacting CoIII-acido systems." @default.
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- W1978359982 date "2003-01-01" @default.
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- W1978359982 title "Reactions ofmer(exo)- andmer(endo)-[Co(dien)(dapo)X]2+ Isomers (X=OH, Cl, ONO2, N3)" @default.
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- W1978359982 doi "https://doi.org/10.1002/hlca.200390004" @default.
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