935658-55-2Relevant academic research and scientific papers
Synthesis and Reactivity of Zirconium and Hafnium Dihydroxophthalocyaninates
Chernii, V.,Fedosova, N.,Kovalska, V.,Selin, R.,Tretyakova, I.
, p. 1489 - 1493 (2020)
Abstract—: Two synthetic approaches for obtaining of zirconium and hafnium dihydroxophthalocyaninates (i.e. (a) that using the zirconium and hafnium alkoxides as the reactive precursors and (b) hydrolysis of zirconium and hafnium dichloridophthalocyaninates) were evaluated. Reactivity of zirconium and hafnium dihydroxophthalocyaninates in their exchange reactions with β-diketones and with decanoic acid was also studied; they were compared with those of zirconium and hafnium dichloridophthalocyaninates. The use of zirconium and hafnium dihydroxophthalocyaninates as the precursors in their reactions with acid-sensitive ligands, such as ketoesters, is found to be a more effective approach.
Synthesis, structure, spectroscopic properties, and electrochemical behavior of mixed ligand bis(β-ketoesterato)zirconium (IV) and -hafnium (IV) phthalocyaninates
Tomachynski, Larisa A.,Chernii, Victor Ya.,Kolotilova, Yulia Yu.,Chernega, Alexander N.,Howard, Judith A.K.,Volkov, Sergey V.
, p. 1493 - 1501 (2008/10/09)
The synthesis of new zirconium and hafnium mixed ligand phthalocyanine complexes PcM(β-ketoester)2, where M-Zr (IV), Hf (IV); Pc - the dianion of phthalocyanine, and β-ketoester - the out planed ligand, is reported. The obtained complexes are characterized by 1H NMR, IR, UV-Vis spectroscopy and cyclic voltammetry. 1H NMR and elemental analysis confirm the substitution of two Cl atoms for two β-ketoester fragments to the central atom of the macrocycle. The data of 1H NMR, UV-Vis spectroscopy have allowed us to conclude that two β-ketoester ligands are in the cis geometry to the phthalocyanine plane. X-ray crystallography for bis(isopropyl 3-oxobutanoato)hafnium(IV)phthalocyanine confirms this conclusion. The central macrocycle of the phthalocyanine ligand is not exactly planar (deviations from the least-square plane exceed 0.15 A?) and has the conformation of an essentially flattened crown. The Hf(1) atom is 1.349(3) above this least-square plane. Cyclic voltammetry investigation shows that the introduction of two β-ketoester ligands to the central atom of phthalocyanine complex leads to both chemical and electrochemical stabilization of the whole Pc system.
