Chloride complex magnetic

LIN/APR] Lincoln, S. F., Aprile, F., Dodgen, FI. W., FFunt, J. P., The exchange of water and chloride ion with nickel(ll)-chloride complexes by nuclear magnetic resonance in concentrated aqueous solutions, Inorg. Chem., 7, (1968), 929-932. Cited on page 141. 

As early as 1967, the chloride complex [FeCl(S2CNEt2)2] was shown to be a molecular ferromagnet (1253). Over the past 20 years a number of further studies have been carried out on the magnetism of this system (and the related bromide), most notably by De Fotis et al. (1254—1258). It has a ferromagnetic transition temperature of 2.457 K, while mixtures of [FeCl(S2CNEt2)2] and [FeBr(S2CNEt2)2] are characterized by transition temperatures of between 2.213 and 1.613 K (1255). 

A 5% solution of chromium trioxide-pyridine complex in dry methylene chloride is prepared. The alcohol (0.01 mole) is dissolved in dry methylene chloride and is added in one portion to the magnetically stirred oxidizing solution (310 ml, a 6 1 mole ratio) at room temperature. The oxidation is complete in 5-15 minutes as indicated by the precipitation of the brownish black chromium reduction products. The mixture is filtered and the solvent is removed (rotary evaporator) leaving the crude product, which may be purified by distillation or recrystallization. Examples are given in Table 1.1. 

Copper(II) complexes of 2,6-lutidylphenylketone thiosemicarbazone, 38, have been prepared from copper(II) chloride and copper(II) bromide [186]. Similar to 2-pyridyl thiosemicarbazones, 38-H coordinates via the ring nitrogen, the azomethine nitrogen and the thiol sulfur based on infrared spectral assignments. Magnetic susceptibilities and electron spin resonance spectra indicate dimeric complexes and both are formulated as [Cu(38-H)A]2 with bridging sulfur atoms. The electronic spectra of both halide complexes show band maxima at 14500-14200 cm with shoulders at 12100 cm S which is consistent with a square pyramidal stereochemistry for a dimeric copper(II) center. 

Ethanol-dimethoxypropane solutions of either 1-formylisoquinoline or 2-formylquinoline thiosemicarbazone and cobalt(II) salts yield [Co(L)A2] complexes where A = Cl, Br, I, NO3, NCS, or NCSe [147]. All are non-electrolytes, have magnetic moments of 4.30-4.70 B.M. and are five coordinate with approximate trigonal bipyramidal stereochemistry involving NNS coordination based on electronic and infrared spectra. [Co(21-H)2] 2H2O was isolated from a cold methanolic solution of cobalt(II) chloride and 1-formylisoquinoline thiosemicarbazone [187]. Infrared spectral studies show NNS coordination the electronic spectral bands fit a distorted octahedral symmetry, and the magnetic moment is 4.48 B.M. 

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