
TY  - JOUR
A1  - Fee, WW 
A1  - McElholum, DE 
A1  - McPherson, AJ 
A1  - Rundle, DL 
T1  - Copper(II)-promoted solvolyses of nickel(II) complexes. I. N,N-Dialkyldithiocarbamates
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1973
VL  - 26
IS  - 6
SP  - 1207
EP  - 1225
KW  - 
UR  - https://doi.org/10.1071/CH9731207 
N2  - The kinetics of copper(II)-promoted solvolyses of bis(N,N- dibutyldithiocarbamato)nickel(II) in dimethyl sulphoxide (dmso), N,N- dimethylacetamide (dma), acetone, and chloroform, and bis(N,N- dicyclohexyldithiocarbamato)nickel(II) in dmso and dma have been examined. Although the reaction stoichiometry differs in chloroform compared with the other solvents, in all media the two-term rate law                     -d[Ni(dtc)2]/dt = (k1+k2[Cu2+])[Ni(dtc)2]   is obeyed. However, in the absence of added sodium and nickel ions, experiments in dmso at low [Cu2+]O, indicate a negligible contribution from the k1 path. Results are discussed in the light of a mechanism involving primary dissociative (k1) and associative (k2) steps. Although the ratios k2/k1 indicate overall importance for the associative pathways of reaction in the low dielectric media cf. dmso and dma, the k1 term also appears as a significant contributor to the reaction of the dibutyldithiocarbamate complex in the former solvents. 
ER  -

