
%0 Journal Article
%A Fee, WW 
%A McElholum, DE 
%A McPherson, AJ 
%A Rundle, DL 
%T Copper(II)-promoted solvolyses of nickel(II) complexes. I. N,N-Dialkyldithiocarbamates
%J Australian Journal of Chemistry
%D 1973/06/01
%V 26
%N 6
%P 1207-1225
%K 
%R https://doi.org/10.1071/CH9731207
%U https://www.publish.csiro.au/paper/CH9731207 
%X 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. 
