Synthesis, Structures, and Solution Behavior of Di- and Trinuclear Titanium(IV)−Cyclophosphato Complexes

The reaction of the cyclotetraphosphate ion (P4O124-) with
[Cp*TiCl3] (Cp* = η5-C5Me5) gives [(Cp*Ti)2(P4O12)2]2- where the
P4O12 ligands adopt a saddle conformation, while that with
[(Cp*TiCl)3(μ-O)3] leads to [(Cp*Ti)3(μ-O)3(P4O12)]- containing a
crown form P4O12 ligand; both products feature their unique cage
structures. On the other hand, the reactions of the cyclotriphosphate
ion (P3O93-) with [(Cp*TiCl2)2(μ-O)] and [(Cp*TiCl)3(μ-O)3] afford
[(Cp*Ti)2(μ-O)(P3O9)2]2- and [(Cp*Ti)3(μ-O)3Cl(P3O9)]-, respectively,
and in both cases the P3O9 ligands bridge two titanium centers
with an η2:η1 mode.