PREPARATIONS STRUCTURES ELECTRONIC SPECTRA AND MAGNETISM OF VANADIUM(3) ALCOHOLATES

Vanadium trichloride is shown to react with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and cyclohexyl alcohols to form alcoholales. As demonstrated by detailed conductance measurements, the complexes when dissolved in the parent alcohol behave as 1:1 electrolytes and should therefore be formulated as [V(ROH)4Cl2]Cl in solution. Their electronic spectra have been recorded and assigned. The complexes isolated from the above solutions may possess not only the formula VCl3.4ROH (with the above structure) but also the formula VCl3.3ROH (these being six-coordinate neutral monomers). The diffuse reflectance spectra of the complexes are compared with the solution spectra and also assigned. The magnetic moments of the complexes have been measured at 12-23 points over the range 321-80°K and the data have been analyzed in terms of the splitting of the ground 3T1g term (in Oh nomenclature) by the asymmetry of the ligand field and in terms of other magnetic parameters. Vanadium-chlorine stretching frequencies occur near 330 cm-1 in these complexes. One bromo complex, [V(i-C3H7OH)4Br2]Br, has also been prepared and studied by the above techniques. It is concluded that alcohols, unlike water and urea, are not able to displace all of the halogen atoms from the first coordination sphere of the parent trihalide. © 1969, American Chemical Society. All rights reserved.