
TY  - JOUR
A1  - Francis, DJ 
A1  - Searle, GH 
T1  - Kinetics of acid-catalysed hydrolysis of the &#945; and &#946; Carbonato(4,7-dimethyltriethylenetetramine) cobalt(III) ions
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1974
VL  - 27
IS  - 2
SP  - 269
EP  - 277
KW  - 
UR  - https://doi.org/10.1071/CH9740269 
N2  - The synthesis and separation of the complexes &#945;-[Co(dmtr)CO3] ClO4 and &#946;-[Co(dmtr)CO3] C1O4,H2O (dmtr = 4,7-dimethyltriethylenetetramine or N,N'-bis(2-aminoethyl)-N,N'-dimethylethane-1,2-diamine) are described. The kinetics of the acid hydrolysis of both complexes, studied in perchloric acid at 25ºC and &#956; = 1.0M (LiC1O4), follow rate laws of form     -d[complex]dt=(k0 + k1[H+I)[complex]  The values of ko and k1 for the K-complex are 1.0 x 10-3 s-1 and 1.8 x 10-2 1. mol-1 s-1 respectively, while for the &#946;-complex the corresponding values are 3.6 x 10-5 s-1 and 5.6 x 10-4 1. mol-1 s-1. Comparisons of these rate constants with the values for similar carbonato(tetramine)cobalt(111) complexes previously studied suggest that the ko path could involve O-C bond cleavage in the present dmtr complexes. The values of the acid dissociation constants of dmtr,4HCl, determined by potentiometric titration, are 1.61, 5.86, 8.18 and 9.95. 
ER  -

