TiCl4-Ether complex
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Figure 2047 shows the EELS recorded with a home-built spectrometer [1], and the energy level diagram and electronic transitions of TiCl4 and TiCl4-2Et2O complex. For TiCl4, there are five prominent peaks 1 to 5 (in red). The first peak at 4.5 eV originates from the transition 1t1 to e, while the second one at 5.4 eV is due to the transition 1t1 to 1t2. The intense peak at 7.4 eV originates from the Rydberg transition 1t1 to 4P. The features at 9.8 and 11.2 eV originate from the transitions from the 1t1 and 3t2 orbitals to the Cl(5P) level.

The spectrum of the TiCl4-2Et2O complex has the transitions at 3.6, 6.7, 7.7, 8.9, and 10.5 eV (in blue). The first peak at 3.6 eV originates from the charge transfer band due to the transition from the highest occupied shifted chlorine lone pair orbital to the Ti4+(3d). The peaks at 6.7 and 7.7 eV are from the transitions from the shifted 1t1 and 3t2 chlorine orbitals to the 4p Rydberg states. This shift is due to the complex formation. The peak at 10.5 eV originates from the 3t2 to 5p transition. Therefore, when the tetrahedral TiCl4 molecule is bonded to form octahedral TiCl4-2Et2O, the molecule should become more ionic. [2] The charge-transfer band in TiCl4 at 4.5 eV is shifted to 3.6 eV because of the change in the electronic structure of the molecule.

EELS, and (b) energy level diagram and the electronic transitions of TiCl4 and TiCl4-2Et2O complex

Figure 2047. (a) The EELS, and (b) The energy level diagram and the electronic transitions of TiCl4 and TiCl4-2Et2O complex. Adapted from [1]



[1] S. P. Ananthavel and M. S. Hegde, Electron States of 1:2 Addition Compounds of TiCl4 with Diethyl Ether and Diethyl Sulfide: HeI Photoelectron and Electron Energy Loss Spectroscopy Studies, J. Phys. Chem. A 1997, 101, 1680-1683.
[2] Huheey, J. E. Inorganic Chemistry; Harper International: Cambridge, 1983; pp 312-315.




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