The electronic spectra of five- and six-co-ordinate complexes of titanium(III) and vanadium(III) halides: a criterion of co-ordination number

Abstract
The complexes MX3,2L (M = Ti or V; X = Cl, Br, or I; L = trimethylamine or α-picoline) have diffuse-reflectance spectra characteristic of five-co-ordinate trigonal-bipyramidal species of D3h symmetry. These spectra are markedly different from those of six-co-ordinate complexes of the type MX3,3L, since the former have characteristic absorption bands in the near-infrared region (10,000–4500 cm.–1). TiCl3,2NMe3, VCl3,2NMe3, and TiCl3,2α-pic dissolve unchanged in the parent ligands. For the trigonal-bipyramidal titanium(III) and vanadium(III) complexes of trimethylamine, ν1 is observed to be more intense than ν2. A possible reason for this is briefly discussed.

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