Electrochemical Synthesis of the Ni(O)-Diazabutadiene Complexes

Article abstract of DOI:10.1002/hlca.19850680131

The electrochemical reduction of Ni salts in the presence of diazabutadiene ligands (DAB= R-N=CH-CH=N-R, R=t-Bu, o-xylyl, p-anisoyl, p-tolyl) has been studied in DMF by cyclic voltammetry and rotating disc polarography.In solutions containing DAB and halide X^-, Ni(II) can be reduced to Ni(DAB)2, and the features of this reduction agree with a mechanism where the second DAB replaces X^- in the coordination sphere of Ni only after its reduction to Ni(O).Rather concentrated (ca. 0.1 M) solutions of NiBr2*DME and DAB in DMF have been electrolyzed without a supporting electrolyte, making the isolation of the product Ni(DAB)2 particularly easy.Thus, gram quantities of Ni(DAB)2 can be conveniently prepared within a few hours.