Abstract
The extent of replacement of the labelled amine protons in the complexes trans-[Co(en)2Cl2]+(en = ethylenediamine) and trans-[Co(ddn)Cl2]+[ddn =(RS)-2,3,2-tet =(RS)-1,9-diamino-3,7-diazanonane] during base hydrolysis has been measured in the substrate and product as a function of the extent of reaction. The results are consistent with a dissociative conjugate-base mechanism and, in the en complex, the ratio of the rate constants for the reprotonation of the conjugate base (k–1) and its dissociation (k2) lies within the range 10 > k–1: k2 > 4. The active conjugate base from the ddn complex has lost a secondary amine proton and 5 > k–1: k2 > 0·5. The anomalously fast base hydrolysis of these complexes arises mainly from the unusually high lability of their conjugate bases. Rate constants for base hydrolysis of the N-deuteriated complexes are compared with those of the untreated complexes
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