Nickel(II) complexes with dithiomalonamide and NN′-diphenyldithiomalonamide
- 1 January 1973
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 879-882
- https://doi.org/10.1039/dt9730000879
Abstract
Dithiomalonamide (HL = Hdtma) and diphenyldithiomalonamide (HL = Hdpma) form diamagnetic planar complexes Ni(dtma)2, Ni(dpma)2, Ni(Hdtma)2X2(X = Cl, Br, I, or ClO4) and Ni(Hdpma)2X2(X = I or ClO4) and paramagnetic octahedral complexes Ni(Hdpma)3X2(X = Cl, Br, or ClO4). NiL2 complexes are non-electrolytes: their electronic spectra in solution and their i.r. spectra in the solid state, both very similar to those of bis(dithioacetylacetonato) nickel(II), the increase in ν(CN), the decrease in ν(CS), and the ν(NiS) frequencies are consistent with a [NiS4] co-ordination. NiL2 form adducts NiL2,nA (nA = 2 MCS, 2 DMF for Hdtma and DMF, 4 DMF, 2 HAc for Hdpma). The splitting orbital parameter Δ1 indicates that these anion ligands assume an intermediate position in the spectrochemical series of sulphur donors. Ni(HL)2X2 and Ni(HL)3X2 are S,N-co-ordinated, as shown by the splitting of the ν(CN) and ν(CS), by their ν(NiN) and ν(NiS) i.r. bands and by the Δ1 values, greater for the Ni(HL)2X2(21 000 cm–1) than for the NiL2(18 000cm–1) complexes. The Δ1 parameters for the Ni(HL)2X2 six-membered ring complexes indicate a ligand strength stronger than in the analogous five-membered ring S,N-co-ordinated complexes of the dithio-oxamides. The distorted octahedral Ni(HL)3X2 complexes have Dq and B values characteristic of [NiS3N3] chromophores.Keywords
This publication has 0 references indexed in Scilit: