Yoneichiro Muto

Magnetic and spectral studies on copper(II) complexes with N-hydroxyalkylsalicylideneimines

Abstract The magnetic properties over the temperature range from 80°–300°K are reported for a number of copper(II) complexes with N-hydroxyalkylsalicylideneimines having empirical formulae (A) Cu(Sal·N·ROH)X and (B) Cu(Sal·N·RO), where Sal·N = · ·C 6 H 4 · H = N·, ROH = CH 2 CH 2 OH, CH 2 CH(CH 3 )OH, C(CH 3 ) 2 CH 2 OH and CH 2 CH 2 CH 2 OH, and X = Cl − , NO 3− and ClO 4− . Their magnetic properties differ depending upon the attached anion X or the R group. Of the (A) type of complexes, Cu(Sal·N·CH 2 CH 2 OH)Cl, Cu(Sal·N·CH 2 CH 2 OH)ClO 4 ·H 2 O and Cu(Sal·N·CH 2 CH(CH 3 )OH) ClO 4 ·C 2 H 5 OH exhibited antiferromagnetic behavior conforming to the Bleaney-Bowers equation, while the other complexes showed normal paramagnetic properties. For the (B) type of complexes, Cu(Sal·N·CH 2 CH 2 CH 2 O) exhibited antiferromagnetic behavior typical of binuclear copper(II) complexes, whereas the other complexes had ferromagnetic properties. The diffuse reflectance and i.r. spectra of these complexes have been measured in order to obtain information about their structure.

Stereochemistries of three types of bi-nuclear copper(II) chloride complexes with N-substituted salicylideneimines☆

The preparation of some bi-nuclear copper(II) chloride complexes with N-substituted salicylideneimines, [Cu(O2.C6H4.(5X|5).C1H − R)Cl]2, where R = alkyl, substituted phenyl groups and (CH2)3OH; and X = H, Cl, CH3 and NO2; and some addition compounds of these with two moles of dimethylformamide (DMF) and dimethylsulfoxide (DMSO) per one dimeric molecule are reported. Measurements of magnetic moments at room temperatures or for some of them temperature variations of magnetic susceptibilities over a temperature range 76°–320°K, reflection spectra at 2000–2340 mμ, and i.r. spectra in rock salt region were recorded for these complexes. These complexes are classified into three types of different stereochemistries based on color and reflection spectra: (1) B-type, brown in color, pseudo-tetrahedral; (2) YG-type, yellow-green, square pyramidal; and (3) Y-type yellow-orange, trigonal-bipyramidal. The empirical rule, “higher energies of d-d bands — lower magnetic moments”, was valid in the B-type complexes. For the Y-type complexes, the existence of electronegative atom or groups seems to be required.

Magnetic and spectral studies on copper(II) halide complexes with N-ethanolsalicylideneimines☆

Abstract In order to investigate which structural factors cause the antiferromagnetic behavior in copper(II) chloride complexes with N-ethanolsalicylideneimine Cu(Sal·N·EtOH)Cl, where SaI·N·EtOH = · O 2 ·C 6 H 4 · C 1 H = N·CH 2 CH 2 OH , the magnetic and spectral properties of a series of copper(II) halide complexes with N-ethanol-5-substituted-salicylideneimines, (H, CH3, Cl and NO2), have been studied. On the basis of their magnetic, i.r. and diffuse reflectance spectral data, we have assigned a chloride-bridged binuclear structure for Cu(Sal·N·EtOH)Cl and Cu(5-CH3·Sal·N·EtOH)Cl, a phenolic oxygen-bridged binuclear structure for Cu(5-CH3·Sal·N·EtOH)-Br·0·1DMF and a phenolic oxygen-bridged linear trimetric structure for Cu3(Sal·N·EtOH)2Cl4·2C2H5OH, where 5CH 3 ·Sal=· O 2 ( C 5 H 3 )·C 6 H 3 · C 1 H= and DMF = N,N-dimethylformamide. Cu2(5-CH3·Sal·N·EtOH)Cl3·0·5H2O exhibited a higher polymeric behavior of antiferromagnetism. All the other complexes obeyed the Curie-Weiss law with very small Weiss constants, θ ≅ −2 ∼ 6°K.