A series of Ni(I1) complexes with methyl-, ethyl-, and sym-dimethyl-, sym-diethyl-, and sym-di-n-butylthioureas and halide, perchlorate, and thiocyanate anions have been prepared and characterized. Spectral and magnetic studies show that compounds NiL4X2 (L = N,N'-dimethyl and N,N'-diethylthiourea, X = halide) are tetragonally distorted octahedral species with a singlet ground state and a thermally populated triplet excited state. The remaining compounds are octahedral. Infrared evidence shows sulfur bonding of the disubstituted ligands to the metal, but suggests nitrogen coordination of the methylthiourea con~pounds.

Fe(thiourea)2(SCN)2, Fe(thiourea)4Cl2, and FeL2Cl2 (where L = methylthiourea, 1,3-dimethylthiourea, and 1,3-diethylthiourea) have been prepared and characterized. Magnetic moments and ligand field spectra indicate that all are octahedral. Infrared spectra show that the thiourea and methylthiourea ligands coordinate through the sulfur atom; the other two ligands are probably sulfur bonded also. The thiocyanate ion is coordinated through the nitrogen.

A number of nickel(l1) coniplexes ~i t h nicthyl-, n-butyl-, phenyl-, and N,N'dimethylurea ligands were prepared with a variety of anions. All exhibited octahedral coordination geometry. Of the anions, only NCS-was in the coordination sphere. Infrared spectral studies indicate coordination of the ligands through oxygen.

Complexes of Co(II), Ni(II), and Zn(I1) with 4-aminoantipyrine and 4-dimethylaminoantipyrine have been prepared and characterized. These contain chloride, bromide, thiocyanate, nitrate, and perchlorate anions. Magnetic, conductivity, and electronic spectral data show that all of the Ni(I1) and Co(I1) complexes have high spin configurations and octahedral geometries, with coordinated halide, thiocyanate, and probably nitrate anions in the respective examples. Infrared analysis indicates that all of the complexes containing C1-, NCS-, and NO3-anions involve chelated 4-aminoantipyrine, whereas the bromide complexes are only bonded to the organic ligands through nitrogen.