Electronic spectra of transition metal complexes. Part I

Ab initio calculations of the ground, excited and ionic states of titanium and vanadium tetrachlorides

“…Three bands are observed in the absorption spectrum of VCU, at 1.1, 3.0, and 4.1 eV. 4 In Td symmetry, transitions from the 2E ground state to 2Ti and 2T2 excited states are dipole allowed. The first excited state we calculate is 2T2 arising from the 3e-10t2 (d-d) transition, 1.4 eV above the ground state.…”

Electronic structure of TiCl4

“…His study shows two absorption bands at 34,840 cm-I and 42,300 cm-' which are attributed to t , + e and t , --f t2 transitions respectively. Alderdice [9] also reports similar absorption maxima in the ultraviolet spectrum of TiCI, . Early attempts to interpret the electronic spectra of transition metal complexes using ligand field theory were made by Ballhausen and Liehr [lo].…”

Complexation and reduction-oxidation equilibriums of titanium chlorides in gaseous aluminum chloride

“…Figure 9 presents log KXi vs. 1/7. Fitting log ' , to a function of the type log K = A + 5/7 + C/T2 (12) we obtain log ATXI = 11.32 -(14.68 X 103)/7 + (4.225 X lO^/T2 (13) with a standard deviation corresponding to 4.7% over the temperature range studied. Since = 0.56, the main complex species is TiAlCl6(g).…”

“…This was found to occur to some extent, and the shoulder at ~1.4 µ 1 (Figure 7) is attributed to this reaction (see next section). However, all experiments with TiCl3(s) in equilibrium with Al2Clé(g) (experiments [11][12][13][14] were carried out at temperatures where Kv (=Ftícu) « 1 (i-e., disproportionation reaction V is strongly shifted to the lefthand side).…”

“…Preparation of KOC(CF3)3 was by reaction of the alcohol with KH in ether at 0 °C, followed by filtration and evaporation of the diethyl ether solvent. 13 Fluorine was passed through a NaF scrubber before use. CsF was dried in a metal reactor at 80 °C under dynamic vacuum for 17 h and then treated with ~2 atm of F2 for several hours.…”