Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones

This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g|| > g⊥ > ge, observed in all the complexes suggests the presence of an unpaired electron in the dx2−y2dx2−y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >CO and NH2 groups whereas, ibh and iinh bond through >CO and >CN groups. The IR spectra of bh and ibh complexes also show HOH stretching and bending modes of coordinated water.