Divalent transition metal complexes of 3,5-pyrazoledicarboxylate

Abstract

New divalent transition metal 3,5-pyrazoledicarboxylate hydrates of empirical formula Mpz(COO)2(H2O)2, where M=Mn, Co, Ni, Cu, Zn and Cd (pz(COO)2=3,5-pyrazoledicarboxylate), metal hydrazine complexes of the type Mpz(COO)2N2H4 where M=Co, Zn or Cd and Mpz(COO)2nN2H4·H2O, where n=1 for M=Ni and n=0.5 for M=Cu have been prepared and characterized by physico-chemical methods. Electronic spectroscopic data suggest that Co and Ni complexes adopt an octahedral geometry. The IR spectra confirm the presence of unidentate carboxylate anion (Δν=νasy(COO–)–νsym(COO–)>215 cm–1) in all the complexes and bidentate bridging hydrazine (νN–N=985–950 cm–1) in the metal hydrazine complexes. Both metal carboxylate and metal hydrazine carboxylate complexes undergo endothermic dehydration and/or dehydrazination followed by exothermic decomposition of organic moiety to give the respective metal oxides as the end products except manganese pyrazoledicarboxylate hydrate, which leaves manganese carbonate. X-ray powder diffraction patterns reveal that the metal carboxylate hydrates are isomorphous as are those of metal hydrazine complexes of cobalt, zinc and cadmium.