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Australian Journal of Chemistry Australian Journal of Chemistry Society
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RESEARCH ARTICLE

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

PJ Nichols and MW Grant

Australian Journal of Chemistry 32(8) 1679 - 1686
Published: 1979

Abstract

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)+ → Ni2+ + Ni(dtc)2.

Analysis of the mechanistic scheme

Ni2+ + dtc ↔ Ni(dtc)2

Ni(dtc)+ + dtc- → Ni(dtc)2

2Ni(dtc)+ → Ni2+ + Ni(dtc)2

gives k1 = 3 × 103 l, mol-1 s-1, k-1 ≈ 0.01 s-1, k2 ≈ 4 × 105 l, mol-1 s-1 and k3 ≈ 1 × 103 l. mol-1 s-1. Coordinated dtc- exerts a significant labilizing effect on coordinated Me2SO molecules in Ni(dtc)+.

https://doi.org/10.1071/CH9791679

© CSIRO 1979

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