A computational study and fragment analysis of the back-bonding in Titanocenyl Complexes containing a five-member L,L′-cyclic ligand, L,L′ = O,O′; S,S′ or Se,Se′

A DFT computational study is performed on different Cp2TiIV(L,L′-BID) complexes with L,L′-BID = dioxolene, dithiolene or diselenolene. A fragment analysis of the titanocene-ligand bonding in the DFT optimized geometries showed that out of plane folding for maximum Ti ← L π donation increases Cp2TiIV(O,O′-BID) (∼35°) < Cp2TiIV(S,S′-BID) (43-49°) < Cp2TiIV(Se,Se′-BID) (48-53°).