From Coordination to Noncoordination: Syntheses and Substitution Lability Studies of Titanium Triflato Complexes.

A new concept for obtaining cationic complexes with triflate counteranions from coordinating triflato ligands was developed. Various routes are leading to titanium(IV) and titanium(III) triflato complexes efficiently. The reactions of pentafulvene titanium complexes with either triflic acid or silver triflate give the corresponding titanium(IV) triflato complexes in excellent yields.

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene Derivatives.

The benzene ligand at CpV(η -C H ) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 a and 2 b) and benzofulvene complexes (3 a and 3 b). The molecular structures of the target compounds suggest a π-η :σ-η coordination mode with a vanadium center.

Crystal structures of the Lewis acid-base adducts {[(CH)N]Ti-}[MeB(CF)]·1.5CH; LB = (CH)PO (1), -F-CHCN (2).

The reaction of [(CH)N]Ti-CH with the Lewis acid B(CF), followed by addition of the Lewis bases (CH)PO and -F-CHCN led to the complex salts tris-(di-cyclo-hexyl-amido)(tri-phenyl-phosphine oxide)titanium methyl-tris(penta-fluoro-phen-yl)borate toluene sesquisolvate, [Ti(CHN)(CHOP)](CHFB)·1.5CH, (), and tris-(di-cyclo-hexyl-amido)(4-fluoro-benzo-nitrile)-titanium methyl-tris-(penta-fluoro-phen-yl)borate toluene sesquisolvate, [Ti(CHN)(CHFN)](CHFB)·1.5CH, (), both crystallizing with 1.