Question

explain the shape of[TiCl6]-3​

Answer 1

Answer:

Getting straight to the point, I believe whichever reference you have that claims D3h is incorrect.

Titanium(III) complexes were the first example presented in my coordination chemistry class to examine the energy difference between the t2g and eg orbitals, explain why it exists and where the colour of coordination compounds derives from including carefully examining the UV spectrum of titanium(III). Our lecturer, Professor Klüfers of the LMU Munich, explained that the hexaaquacomplex is practically octahedral in shape. However, there is not just a clean absorption band but rather a band with a shoulder. This is because the excited state of [Ti(H2O)6]3+ is Jahn–Teller distorted, having an uneven eg population, meaning that two slightly different excitation energies exist.

One might go a step further and argue that even in the ground state a certain distortion should exist. If one were to pull (not push) the ligands in z-direction slightly closer to the central metal, this would destabilise any orbitals with z contribution meaning that dxy suddenly becomes the single most stable d orbital. This slight distortion which one might call anti-Jahn–Teller (since it is opposite to the classic Jahn–Teller distortion) could explain a reduction of symmetry from Oh to D4h.

D3h symmetry is not consistent with octahedraloid coordination spheres at all. It is very common for pentacoordinated centres such as PF5. The only way to have six ligands — as in hexachloridotitanate(III) — around a central metal in this point group would be a trigonal prism. That would be a very uncommon coordination sphere and I am sure I would have heard of it in the context of titanium(III) in said course above should it exist for this species. Indeed, the source orthocresol found and linked in the comments makes no mention of any distorted geometry at all: