Out of line? Theory predicts that [Ti(N3)4] should exhibit unprecedented linear TiNNN bond angles as a consequence of the α-N atoms of the azide groups acting as tridentate donors into the empty tetrahedral d0 orbitals of a (+IV) Group 4 metal atom. The title compounds were prepared and characterized (see structure). They do not possess linear TiNNN angles because their coordination numbers exceed four.
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Haiges et al. (2004) studied this question.