Complex halides of transition metals. Part X. Reaction of molten diethylammonium chloride with titanium(III), vanadium(III), and chromium(III) chlorides: a spectroscopic and magnetic study of the TiCl63–, Ti2Cl93–, V2Cl93–, and Cr2Cl93– anions

Abstract

From the reaction of titanium(III), vanadium(III), and chromium(III) chloride with molten diethylammonium chloride the complex anions TiCl₆^3–, Ti₂Cl₉^3–, V₂Cl₉^3–, and Cr₂Cl₉^3– were isolated. The electronic absorption spectra and temperature-range magnetic properties of these complexes have been measured and these data are compared with results of earlier studies on alkali-metal salts of the M₂Cl₉^3– anions. In particular, the effect of varying the cation upon any antiferromagnetic interaction within the binuclear M₂Cl₉^3– anions is investigated. The far-i.r. (500–200 cm.^–1) and Raman spectra of the TiCl₆^3– anion are also reported and the ν₁, ν₂, ν₃, and ν₅ fundamentals assigned. The electron-transfer spectrum of this same anion is also assigned and the optical electronegativity parameter χ_opt for Ti^III calculated to be 1·85. The titanium(III) complex [C₅H₆N]₃TiCl₆ is formed when titanium(II) chloride reacts with molten pyridinium hydrochloride.