Fulvalenes titanium complexes

The ionic fulvalene titanium complex [ CpTi(H2O) 2(/i-Ci0H8)(/i-O)]2+[OTP]2 l/2THF (Scheme 591) can be prepared as an air stable compound by the reaction of binuclear [CpTi(/i-H)]2(//-C10H8) with trifluoromethane-sulphonic acid in the presence of small amounts of water. A reaction intermediate is [TiCp(OTf)2]2(//-Ci0H8). The molecular structure of the fi-oxo aquo fulvalene complex has been confirmed by X-ray crystallography.1534... 

Hydrolysis of titanocene produces the complex [Cp(C5H4)TiOH]2 X-ray crystallography has established that this has the fulvalene structure (1) characteristic of the titanocene molecule (Vol. 4, p. 2) and that the titanium atoms are bridged by the two hydroxy-groups/ ... 

The titanium fulvalene complex 113 was prepared by Roesky et al. from bis(cyclopentadienyl)difluorotitanium(IV) by treatment with l.Sequiv. of potassium at elevated temperature (Scheme 10.39). Although there is no li-Ti bond, the fulvalene ligand is bent by 15.3° [114]. Other dinuclear titanium fulvalene complexes were reported by Thewalt etal. [115]. 

---