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Spectrophotometric study of nitrate and bromo-nitrate-Ni(II) complexes in acetone

T. Šramko

Slovak Technical University, Bratislava

 

Abstract: Spectrophotometric studies of the systems Ni(ClO4)2.6H2O-LiNO3- Me2CO (1) and Ni(ClO4)2.6H2O-LiNO3-LiBr-Me2CO (2) indicated formation of several nitrate-Ni(II) and bromonitrate-Ni(II) complexes. The octahedral nitrate-Ni complexes showed ratios of Ni:NO3 = 1:1, 1:2, and higher. These complexes are coordinatively satd. by the mol. of the solvent. Application of the isomolar-series method indicated that the presence of the nitrate ion as a ligand in the inner Ni (II) coordination sphere stabilizes the proportions of Ni:Br:NO3 as 1:1:1 and 1:1:2. It is assumed that the heterocomplexes of Ni(II) ligated with nitrate or bromine ions are coordinatively satd. and have the octahedral structure. Equil. changes in 1 and 2 with molar ratios Ni:Br = 1:1, 1:1.5, 1:3, and 1:4 were investigated by using the methods of univariant-change and spectroscopy. Existence of disproportional equil. of the soln. of NiBr2 in acetone was demonstrated and proved that the formation of the heterocomplexes Ni-Br-NO3 is influenced by substitution of the solvent in the [NiBr (solvent)n]+ complex.

Full paper in Portable Document Format: 176a390.pdf (in Slovak)

 

Chemical Papers 17 (6) 390–401 (1963)

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