
TY  - JOUR
A1  - Nichols, PJ 
A1  - Grant, MW 
T1  - The Kinetics and Mechanism of a Reaction in Which Ligand Substitution is Accompanied by a Spin-State Change: Observation of the Elusive Monodithiocarbamatonickel(II) Complex in Dimethyl Sulfoxide
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1979
VL  - 32
IS  - 8
SP  - 1679
EP  - 1686
KW  - 
UR  - https://doi.org/10.1071/CH9791679 
N2  - In solutions in Me2SO containing low concentrations of diethyldithiocarbamate ion (dtc-) and very high concentrations of Ni(Me2SO)62+ ion, the hitherto undetected Ni(dtc)+ complex is kinetically stabilized and its electronic spectrum can be recorded. The mono complex is thermodynamically unstable and is converted into Ni(dtc)2 by two independent pathways, one involving direct reaction between Ni(dtc)+ and dtc-, the other being a dimerization reaction, 2Ni(dtc)+ &#8594; Ni2+ + Ni(dtc)2.  Analysis of the mechanistic scheme Ni2+ + dtc &#8596; Ni(dtc)2 Ni(dtc)+ + dtc- &#8594; Ni(dtc)2 2Ni(dtc)+ &#8594; Ni2+ + Ni(dtc)2 gives k1 = 3 &#215; 103 l, mol-1 s-1, k-1 &#8776; 0.01 s-1, k2 &#8776; 4 &#215; 105 l, mol-1 s-1 and k3 &#8776; 1 &#215; 103 l. mol-1 s-1. Coordinated dtc- exerts a significant labilizing effect on coordinated Me2SO molecules in Ni(dtc)+. 
ER  -

